<?xml version="1.0" encoding="US-ASCII"?>
<!--XBRL Document Created with Wdesk from Workiva-->
<!-- -->
<xsd:schema attributeFormDefault="unqualified" elementFormDefault="qualified" targetNamespace="http://www.valero.com/20190930" xmlns:link="http://www.xbrl.org/2003/linkbase" xmlns:nonnum="http://www.xbrl.org/dtr/type/non-numeric" xmlns:num="http://www.xbrl.org/dtr/type/numeric" xmlns:us-types="http://fasb.org/us-types/2019-01-31" xmlns:vlo="http://www.valero.com/20190930" xmlns:xbrli="http://www.xbrl.org/2003/instance" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:xsd="http://www.w3.org/2001/XMLSchema">
  <xsd:import namespace="http://fasb.org/srt-types/2019-01-31" schemaLocation="http://xbrl.fasb.org/srt/2019/elts/srt-types-2019-01-31.xsd" />
  <xsd:import namespace="http://fasb.org/srt/2019-01-31" schemaLocation="http://xbrl.fasb.org/srt/2019/elts/srt-2019-01-31.xsd" />
  <xsd:import namespace="http://fasb.org/us-gaap/2019-01-31" schemaLocation="http://xbrl.fasb.org/us-gaap/2019/elts/us-gaap-2019-01-31.xsd" />
  <xsd:import namespace="http://fasb.org/us-roles/2019-01-31" schemaLocation="http://xbrl.fasb.org/us-gaap/2019/elts/us-roles-2019-01-31.xsd" />
  <xsd:import namespace="http://fasb.org/us-types/2019-01-31" schemaLocation="http://xbrl.fasb.org/us-gaap/2019/elts/us-types-2019-01-31.xsd" />
  <xsd:import namespace="http://www.xbrl.org/2003/instance" schemaLocation="http://www.xbrl.org/2003/xbrl-instance-2003-12-31.xsd" />
  <xsd:import namespace="http://www.xbrl.org/2003/linkbase" schemaLocation="http://www.xbrl.org/2003/xbrl-linkbase-2003-12-31.xsd" />
  <xsd:import namespace="http://www.xbrl.org/2009/arcrole/fact-explanatoryFact" schemaLocation="http://www.xbrl.org/lrr/arcrole/factExplanatory-2009-12-16.xsd" />
  <xsd:import namespace="http://www.xbrl.org/2009/role/negated" schemaLocation="http://www.xbrl.org/lrr/role/negated-2009-12-16.xsd" />
  <xsd:import namespace="http://www.xbrl.org/2009/role/net" schemaLocation="http://www.xbrl.org/lrr/role/net-2009-12-16.xsd" />
  <xsd:import namespace="http://www.xbrl.org/dtr/type/non-numeric" schemaLocation="http://www.xbrl.org/dtr/type/nonNumeric-2009-12-16.xsd" />
  <xsd:import namespace="http://www.xbrl.org/dtr/type/numeric" schemaLocation="http://www.xbrl.org/dtr/type/numeric-2009-12-16.xsd" />
  <xsd:import namespace="http://xbrl.org/2005/xbrldt" schemaLocation="http://www.xbrl.org/2005/xbrldt-2005.xsd" />
  <xsd:import namespace="http://xbrl.sec.gov/country/2017-01-31" schemaLocation="https://xbrl.sec.gov/country/2017/country-2017-01-31.xsd" />
  <xsd:import namespace="http://xbrl.sec.gov/currency/2019-01-31" schemaLocation="https://xbrl.sec.gov/currency/2019/currency-2019-01-31.xsd" />
  <xsd:import namespace="http://xbrl.sec.gov/dei/2019-01-31" schemaLocation="https://xbrl.sec.gov/dei/2019/dei-2019-01-31.xsd" />
  <xsd:import namespace="http://xbrl.sec.gov/exch/2019-01-31" schemaLocation="https://xbrl.sec.gov/exch/2019/exch-2019-01-31.xsd" />
  <xsd:import namespace="http://xbrl.sec.gov/invest/2013-01-31" schemaLocation="http://xbrl.sec.gov/invest/2013/invest-2013-01-31.xsd" />
  <xsd:import namespace="http://xbrl.sec.gov/naics/2017-01-31" schemaLocation="http://xbrl.sec.gov/naics/2017/naics-2017-01-31.xsd" />
  <xsd:import namespace="http://xbrl.sec.gov/sic/2011-01-31" schemaLocation="http://xbrl.sec.gov/sic/2011/sic-2011-01-31.xsd" />
  <xsd:import namespace="http://xbrl.sec.gov/stpr/2018-01-31" schemaLocation="https://xbrl.sec.gov/stpr/2018/stpr-2018-01-31.xsd" />
  <xsd:annotation>
    <xsd:appinfo>
      <link:linkbaseRef xlink:arcrole="http://www.w3.org/1999/xlink/properties/linkbase" xlink:href="vlo-20190930_cal.xml" xlink:role="http://www.xbrl.org/2003/role/calculationLinkbaseRef" xlink:type="simple" />
      <link:linkbaseRef xlink:arcrole="http://www.w3.org/1999/xlink/properties/linkbase" xlink:href="vlo-20190930_def.xml" xlink:role="http://www.xbrl.org/2003/role/definitionLinkbaseRef" xlink:type="simple" />
      <link:linkbaseRef xlink:arcrole="http://www.w3.org/1999/xlink/properties/linkbase" xlink:href="vlo-20190930_lab.xml" xlink:role="http://www.xbrl.org/2003/role/labelLinkbaseRef" xlink:type="simple" />
      <link:linkbaseRef xlink:arcrole="http://www.w3.org/1999/xlink/properties/linkbase" xlink:href="vlo-20190930_pre.xml" xlink:role="http://www.xbrl.org/2003/role/presentationLinkbaseRef" xlink:type="simple" />
      <link:roleType id="BasisOfPresentationAndSignificantAccountingPolicies" roleURI="http://www.valero.com/role/BasisOfPresentationAndSignificantAccountingPolicies">
        <link:definition>2101100 - Disclosure - Basis of Presentation and Significant Accounting Policies</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="BasisOfPresentationAndSignificantAccountingPoliciesDetails" roleURI="http://www.valero.com/role/BasisOfPresentationAndSignificantAccountingPoliciesDetails">
        <link:definition>2401403 - Disclosure - Basis of Presentation and Significant Accounting Policies (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="BasisOfPresentationAndSignificantAccountingPoliciesPolicies" roleURI="http://www.valero.com/role/BasisOfPresentationAndSignificantAccountingPoliciesPolicies">
        <link:definition>2201201 - Disclosure - Basis of Presentation and Significant Accounting Policies (Policies)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="BasisOfPresentationAndSignificantAccountingPoliciesTables" roleURI="http://www.valero.com/role/BasisOfPresentationAndSignificantAccountingPoliciesTables">
        <link:definition>2301302 - Disclosure - Basis of Presentation and Significant Accounting Policies (Tables)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="CommitmentsAndContingencies" roleURI="http://www.valero.com/role/CommitmentsAndContingencies">
        <link:definition>2120100 - Disclosure - Commitments and Contingencies</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="CommitmentsAndContingenciesDetails" roleURI="http://www.valero.com/role/CommitmentsAndContingenciesDetails">
        <link:definition>2420401 - Disclosure - Commitments and Contingencies (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="CondensedConsolidatingFinancialStatements" roleURI="http://www.valero.com/role/CondensedConsolidatingFinancialStatements">
        <link:definition>2129100 - Disclosure - Condensed Consolidating Financial Statements</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="CondensedConsolidatingFinancialStatementsBalanceSheetDetails" roleURI="http://www.valero.com/role/CondensedConsolidatingFinancialStatementsBalanceSheetDetails">
        <link:definition>2429403 - Disclosure - Condensed Consolidating Financial Statements, Balance Sheet (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="CondensedConsolidatingFinancialStatementsDetails" roleURI="http://www.valero.com/role/CondensedConsolidatingFinancialStatementsDetails">
        <link:definition>2429402 - Disclosure - Condensed Consolidating Financial Statements (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="CondensedConsolidatingFinancialStatementsStatementOfCashFlowsDetails" roleURI="http://www.valero.com/role/CondensedConsolidatingFinancialStatementsStatementOfCashFlowsDetails">
        <link:definition>2429406 - Disclosure - Condensed Consolidating Financial Statements, Statement of Cash Flows (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="CondensedConsolidatingFinancialStatementsStatementOfComprehensiveIncomeDetails" roleURI="http://www.valero.com/role/CondensedConsolidatingFinancialStatementsStatementOfComprehensiveIncomeDetails">
        <link:definition>2429405 - Disclosure - Condensed Consolidating Financial Statements, Statement of Comprehensive Income (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="CondensedConsolidatingFinancialStatementsStatementOfIncomeDetails" roleURI="http://www.valero.com/role/CondensedConsolidatingFinancialStatementsStatementOfIncomeDetails">
        <link:definition>2429404 - Disclosure - Condensed Consolidating Financial Statements, Statement of Income (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="CondensedConsolidatingFinancialStatementsTables" roleURI="http://www.valero.com/role/CondensedConsolidatingFinancialStatementsTables">
        <link:definition>2329301 - Disclosure - Condensed Consolidating Financial Statements (Tables)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="ConsolidatedBalanceSheets" roleURI="http://www.valero.com/role/ConsolidatedBalanceSheets">
        <link:definition>1001000 - Statement - Consolidated Balance Sheets</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="ConsolidatedBalanceSheetsParenthetical" roleURI="http://www.valero.com/role/ConsolidatedBalanceSheetsParenthetical">
        <link:definition>1001001 - Statement - Consolidated Balance Sheets (Parenthetical)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="ConsolidatedStatementsOfCashFlowsUnaudited" roleURI="http://www.valero.com/role/ConsolidatedStatementsOfCashFlowsUnaudited">
        <link:definition>1010000 - Statement - Consolidated Statements of Cash Flows (unaudited)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="ConsolidatedStatementsOfComprehensiveIncomeUnaudited" roleURI="http://www.valero.com/role/ConsolidatedStatementsOfComprehensiveIncomeUnaudited">
        <link:definition>1007000 - Statement - Consolidated Statements of Comprehensive Income (unaudited)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="ConsolidatedStatementsOfEquityUnaudited" roleURI="http://www.valero.com/role/ConsolidatedStatementsOfEquityUnaudited">
        <link:definition>1009000 - Statement - Consolidated Statements of Equity (unaudited)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="ConsolidatedStatementsOfEquityUnauditedParenthetical" roleURI="http://www.valero.com/role/ConsolidatedStatementsOfEquityUnauditedParenthetical">
        <link:definition>1009501 - Statement - Consolidated Statements of Equity (unaudited) (Parenthetical)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="ConsolidatedStatementsOfIncomeUnaudited" roleURI="http://www.valero.com/role/ConsolidatedStatementsOfIncomeUnaudited">
        <link:definition>1004000 - Statement - Consolidated Statements of Income (unaudited)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="Debt" roleURI="http://www.valero.com/role/Debt">
        <link:definition>2119100 - Disclosure - Debt</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="DebtCreditFacilitiesDetails" roleURI="http://www.valero.com/role/DebtCreditFacilitiesDetails">
        <link:definition>2419403 - Disclosure - Debt, Credit Facilities (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="DebtInterestIncurredDetails" roleURI="http://www.valero.com/role/DebtInterestIncurredDetails">
        <link:definition>2419404 - Disclosure - Debt, Interest Incurred (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="DebtNarrativeDetails" roleURI="http://www.valero.com/role/DebtNarrativeDetails">
        <link:definition>2419402 - Disclosure - Debt, Narrative (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="DebtTables" roleURI="http://www.valero.com/role/DebtTables">
        <link:definition>2319301 - Disclosure - Debt (Tables)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="DocumentAndEntityInformation" roleURI="http://www.valero.com/role/DocumentAndEntityInformation">
        <link:definition>0001000 - Document - Document and Entity Information</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="EarningsPerCommonShare" roleURI="http://www.valero.com/role/EarningsPerCommonShare">
        <link:definition>2124100 - Disclosure - Earnings Per Common Share</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="EarningsPerCommonShareDetails" roleURI="http://www.valero.com/role/EarningsPerCommonShareDetails">
        <link:definition>2424402 - Disclosure - Earnings Per Common Share (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="EarningsPerCommonShareTables" roleURI="http://www.valero.com/role/EarningsPerCommonShareTables">
        <link:definition>2324301 - Disclosure - Earnings Per Common Share (Tables)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="EmployeeBenefitPlans" roleURI="http://www.valero.com/role/EmployeeBenefitPlans">
        <link:definition>2123100 - Disclosure - Employee Benefit Plans</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="EmployeeBenefitPlansDetails" roleURI="http://www.valero.com/role/EmployeeBenefitPlansDetails">
        <link:definition>2423402 - Disclosure - Employee Benefit Plans (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="EmployeeBenefitPlansTables" roleURI="http://www.valero.com/role/EmployeeBenefitPlansTables">
        <link:definition>2323301 - Disclosure - Employee Benefit Plans (Tables)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="Equity" roleURI="http://www.valero.com/role/Equity">
        <link:definition>2121100 - Disclosure - Equity</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="EquityChangesInAccumulatedOtherComprehensiveLossDetails" roleURI="http://www.valero.com/role/EquityChangesInAccumulatedOtherComprehensiveLossDetails">
        <link:definition>2421404 - Disclosure - Equity, Changes in Accumulated Other Comprehensive Loss (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="EquityNarrativeDetails" roleURI="http://www.valero.com/role/EquityNarrativeDetails">
        <link:definition>2421403 - Disclosure - Equity, Narrative (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="EquityShareActivityRollforwardDetails" roleURI="http://www.valero.com/role/EquityShareActivityRollforwardDetails">
        <link:definition>2421402 - Disclosure - Equity, Share Activity Rollforward (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="EquityTables" roleURI="http://www.valero.com/role/EquityTables">
        <link:definition>2321301 - Disclosure - Equity (Tables)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="FairValueMeasurements" roleURI="http://www.valero.com/role/FairValueMeasurements">
        <link:definition>2127100 - Disclosure - Fair Value Measurements</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="FairValueMeasurementsNonrecurringDetails" roleURI="http://www.valero.com/role/FairValueMeasurementsNonrecurringDetails">
        <link:definition>2427403 - Disclosure - Fair Value Measurements, Nonrecurring (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="FairValueMeasurementsOtherFinancialInstrumentsDetails" roleURI="http://www.valero.com/role/FairValueMeasurementsOtherFinancialInstrumentsDetails">
        <link:definition>2427404 - Disclosure - Fair Value Measurements, Other Financial Instruments (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="FairValueMeasurementsRecurringDetails" roleURI="http://www.valero.com/role/FairValueMeasurementsRecurringDetails">
        <link:definition>2427402 - Disclosure - Fair Value Measurements, Recurring (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="FairValueMeasurementsTables" roleURI="http://www.valero.com/role/FairValueMeasurementsTables">
        <link:definition>2327301 - Disclosure - Fair Value Measurements (Tables)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="Inventories" roleURI="http://www.valero.com/role/Inventories">
        <link:definition>2117100 - Disclosure - Inventories</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="InventoriesDetails" roleURI="http://www.valero.com/role/InventoriesDetails">
        <link:definition>2417402 - Disclosure - Inventories (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="InventoriesTables" roleURI="http://www.valero.com/role/InventoriesTables">
        <link:definition>2317301 - Disclosure - Inventories (Tables)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="Leases" roleURI="http://www.valero.com/role/Leases">
        <link:definition>2118100 - Disclosure - Leases</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="LeasesAdditionalInformationDetails" roleURI="http://www.valero.com/role/LeasesAdditionalInformationDetails">
        <link:definition>2418404 - Disclosure - Leases, Additional Information (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="LeasesFutureLeaseCommencementDetails" roleURI="http://www.valero.com/role/LeasesFutureLeaseCommencementDetails">
        <link:definition>2418406 - Disclosure - Leases, Future Lease Commencement (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="LeasesRemainingMinimumLeasePaymentsDetails" roleURI="http://www.valero.com/role/LeasesRemainingMinimumLeasePaymentsDetails">
        <link:definition>2418405 - Disclosure - Leases, Remaining Minimum Lease Payments (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="LeasesRemainingMinimumLeasePaymentsDetailsCalc2" roleURI="http://www.valero.com/role/LeasesRemainingMinimumLeasePaymentsDetailsCalc2">
        <link:definition>2418405 - Disclosure - Leases, Remaining Minimum Lease Payments (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="LeasesRentalExpenseNetOfSubleaseRentalIncomeDetails" roleURI="http://www.valero.com/role/LeasesRentalExpenseNetOfSubleaseRentalIncomeDetails">
        <link:definition>2418403 - Disclosure - Leases, Rental Expense, Net of Sublease Rental Income (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="LeasesTables" roleURI="http://www.valero.com/role/LeasesTables">
        <link:definition>2318301 - Disclosure - Leases (Tables)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="LeasesTotalLeaseCostByClassOfUnderlyingAssetDetails" roleURI="http://www.valero.com/role/LeasesTotalLeaseCostByClassOfUnderlyingAssetDetails">
        <link:definition>2418402 - Disclosure - Leases, Total Lease Cost by Class of Underlying Asset (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="MergerAndAcquisition" roleURI="http://www.valero.com/role/MergerAndAcquisition">
        <link:definition>2102100 - Disclosure - Merger and Acquisition</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="MergerAndAcquisitionDetails" roleURI="http://www.valero.com/role/MergerAndAcquisitionDetails">
        <link:definition>2402401 - Disclosure - Merger and Acquisition (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="PriceRiskManagementActivities" roleURI="http://www.valero.com/role/PriceRiskManagementActivities">
        <link:definition>2128100 - Disclosure - Price Risk Management Activities</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="PriceRiskManagementActivitiesDetails" roleURI="http://www.valero.com/role/PriceRiskManagementActivitiesDetails">
        <link:definition>2428402 - Disclosure - Price Risk Management Activities (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="PriceRiskManagementActivitiesEffectOfDerivativeInstrumentsOnIncomeDetails" roleURI="http://www.valero.com/role/PriceRiskManagementActivitiesEffectOfDerivativeInstrumentsOnIncomeDetails">
        <link:definition>2428404 - Disclosure - Price Risk Management Activities, Effect of Derivative Instruments on Income (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="PriceRiskManagementActivitiesHedgingInstrumentsByConsolidatedBalanceSheetLocationDetails" roleURI="http://www.valero.com/role/PriceRiskManagementActivitiesHedgingInstrumentsByConsolidatedBalanceSheetLocationDetails">
        <link:definition>2428403 - Disclosure - Price Risk Management Activities, Hedging Instruments by Consolidated Balance Sheet Location (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="PriceRiskManagementActivitiesTables" roleURI="http://www.valero.com/role/PriceRiskManagementActivitiesTables">
        <link:definition>2328301 - Disclosure - Price Risk Management Activities (Tables)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="RevenuesAndSegmentInformation" roleURI="http://www.valero.com/role/RevenuesAndSegmentInformation">
        <link:definition>2125100 - Disclosure - Revenues and Segment Information</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="RevenuesAndSegmentInformationAssetsDetails" roleURI="http://www.valero.com/role/RevenuesAndSegmentInformationAssetsDetails">
        <link:definition>2425405 - Disclosure - Revenues and Segment Information, Assets (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="RevenuesAndSegmentInformationComponentsOfOperatingIncomeLossDetails" roleURI="http://www.valero.com/role/RevenuesAndSegmentInformationComponentsOfOperatingIncomeLossDetails">
        <link:definition>2425403 - Disclosure - Revenues and Segment Information, Components of Operating Income (Loss) (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="RevenuesAndSegmentInformationDisaggregationOfRevenueByProductDetails" roleURI="http://www.valero.com/role/RevenuesAndSegmentInformationDisaggregationOfRevenueByProductDetails">
        <link:definition>2425404 - Disclosure - Revenues and Segment Information, Disaggregation of Revenue by Product (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="RevenuesAndSegmentInformationReceivablesFromContractsWithCustomersDetails" roleURI="http://www.valero.com/role/RevenuesAndSegmentInformationReceivablesFromContractsWithCustomersDetails">
        <link:definition>2425402 - Disclosure - Revenues and Segment Information, Receivables from Contracts with Customers (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="RevenuesAndSegmentInformationTables" roleURI="http://www.valero.com/role/RevenuesAndSegmentInformationTables">
        <link:definition>2325301 - Disclosure - Revenues and Segment Information (Tables)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="SupplementalCashFlowInformation" roleURI="http://www.valero.com/role/SupplementalCashFlowInformation">
        <link:definition>2126100 - Disclosure - Supplemental Cash Flow Information</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="SupplementalCashFlowInformationDetails" roleURI="http://www.valero.com/role/SupplementalCashFlowInformationDetails">
        <link:definition>2426402 - Disclosure - Supplemental Cash Flow Information (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="SupplementalCashFlowInformationTables" roleURI="http://www.valero.com/role/SupplementalCashFlowInformationTables">
        <link:definition>2326301 - Disclosure - Supplemental Cash Flow Information (Tables)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="VariableInterestEntities" roleURI="http://www.valero.com/role/VariableInterestEntities">
        <link:definition>2122100 - Disclosure - Variable Interest Entities</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="VariableInterestEntitiesDetails" roleURI="http://www.valero.com/role/VariableInterestEntitiesDetails">
        <link:definition>2422402 - Disclosure - Variable Interest Entities (Details)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
      <link:roleType id="VariableInterestEntitiesTables" roleURI="http://www.valero.com/role/VariableInterestEntitiesTables">
        <link:definition>2322301 - Disclosure - Variable Interest Entities (Tables)</link:definition>
        <link:usedOn>link:presentationLink</link:usedOn>
        <link:usedOn>link:calculationLink</link:usedOn>
        <link:usedOn>link:definitionLink</link:usedOn>
      </link:roleType>
    </xsd:appinfo>
  </xsd:annotation>
  <xsd:element abstract="true" id="vlo_ARSalesFacilityMember" name="ARSalesFacilityMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element id="vlo_AccruedLiabilitiesRelatedPartiesCurrent" name="AccruedLiabilitiesRelatedPartiesCurrent" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="credit" xbrli:periodType="instant" />
  <xsd:element id="vlo_AssetsFairValueDisclosureGrossLiabilityandObligationtoReturnCashOffsetNet" name="AssetsFairValueDisclosureGrossLiabilityandObligationtoReturnCashOffsetNet" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="debit" xbrli:periodType="instant" />
  <xsd:element id="vlo_AssetsandLiabilitiesLesseeTableTextBlock" name="AssetsandLiabilitiesLesseeTableTextBlock" nillable="true" substitutionGroup="xbrli:item" type="nonnum:textBlockItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_CanadianRevolverLetterOfCreditMember" name="CanadianRevolverLetterOfCreditMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_CanadianRevolverMember" name="CanadianRevolverMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_CashFlowsRelatedToInterestAndIncomeTaxesAbstract" name="CashFlowsRelatedToInterestAndIncomeTaxesAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_CentralMexicoTerminalsMember" name="CentralMexicoTerminalsMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_CentralTexasPipelineMember" name="CentralTexasPipelineMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_CommittedLetterofCreditFacilityExpiresNovemberMember" name="CommittedLetterofCreditFacilityExpiresNovemberMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element id="vlo_ConsiderationTransferredWorkingCapitalNetofCashAcquired" name="ConsiderationTransferredWorkingCapitalNetofCashAcquired" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="credit" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_CorporateReconcilingItemsAndEliminationsMember" name="CorporateReconcilingItemsAndEliminationsMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_CurrentLeaseLiabilitiesReflectedInTheFollowingBalanceSheetLineItemsFinanceLeaseAbstract" name="CurrentLeaseLiabilitiesReflectedInTheFollowingBalanceSheetLineItemsFinanceLeaseAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_CurrentLeaseLiabilitiesReflectedInTheFollowingBalanceSheetLineItemsOperatingLeaseAbstract" name="CurrentLeaseLiabilitiesReflectedInTheFollowingBalanceSheetLineItemsOperatingLeaseAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_DefinedBenefitPlanAssetsHeldinTrustMember" name="DefinedBenefitPlanAssetsHeldinTrustMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element id="vlo_DefinedBenefitPlanPlanAssetsEmployerDiscretionaryContributionAmount" name="DefinedBenefitPlanPlanAssetsEmployerDiscretionaryContributionAmount" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="debit" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_DiamondGreenDieselHoldingsLLCMember" name="DiamondGreenDieselHoldingsLLCMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_DistillatesMember" name="DistillatesMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_DistillersGrainsMember" name="DistillersGrainsMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element id="vlo_DurationofRenewalOption" name="DurationofRenewalOption" nillable="true" substitutionGroup="xbrli:item" type="xbrli:durationItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_EmployeeBenefitPlansTextualAbstract" name="EmployeeBenefitPlansTextualAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_EnergyandGasesMember" name="EnergyandGasesMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element id="vlo_EthanolFeedstocksAndProducts" name="EthanolFeedstocksAndProducts" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="debit" xbrli:periodType="instant" />
  <xsd:element abstract="true" id="vlo_EthanolMember" name="EthanolMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_EthanolProductMember" name="EthanolProductMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element id="vlo_FairValueConcentrationOfRiskCollateralPolicyPolicyTextBlock" name="FairValueConcentrationOfRiskCollateralPolicyPolicyTextBlock" nillable="true" substitutionGroup="xbrli:item" type="nonnum:textBlockItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_FairValueMeasurementsTextualAbstract" name="FairValueMeasurementsTextualAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_FeedstockProcessingEquipmentMember" name="FeedstockProcessingEquipmentMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_FinanceLeaseAssetsAndLiabilitiesLesseeAbstract" name="FinanceLeaseAssetsAndLiabilitiesLesseeAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_FinanceLeaseCashFlowLesseeAbstract" name="FinanceLeaseCashFlowLesseeAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_FinanceLeaseLesseeOtherSupplementalInformationAbstract" name="FinanceLeaseLesseeOtherSupplementalInformationAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element id="vlo_FinancialandNonfinancialLiabilitiesFairValueDisclosureGrossAssetandRighttoReclaimCashOffsetNet" name="FinancialandNonfinancialLiabilitiesFairValueDisclosureGrossAssetandRighttoReclaimCashOffsetNet" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="credit" xbrli:periodType="instant" />
  <xsd:element abstract="true" id="vlo_ForeignExchangeContractUSDollarEquivalentCanadianDollarsMember" name="ForeignExchangeContractUSDollarEquivalentCanadianDollarsMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_ForeignExchangeContractUSDollarEquivalentPoundsSterlingMember" name="ForeignExchangeContractUSDollarEquivalentPoundsSterlingMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_ForeignExchangeContractUSDollarsMember" name="ForeignExchangeContractUSDollarsMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_ForwardContractsMaturityCurrentYearMember" name="ForwardContractsMaturityCurrentYearMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_ForwardContractsMaturityYearTwoMember" name="ForwardContractsMaturityYearTwoMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_FutureMaturityCurrentYearMember" name="FutureMaturityCurrentYearMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_FutureMaturityYearTwoMember" name="FutureMaturityYearTwoMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_GasolineAndBlendstocksMember" name="GasolineAndBlendstocksMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_GrainInBushelsMember" name="GrainInBushelsMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_IEnovaRevolverMember" name="IEnovaRevolverMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element id="vlo_IntercompanyFinancingActivities" name="IntercompanyFinancingActivities" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="debit" xbrli:periodType="duration" />
  <xsd:element id="vlo_IntercompanyInvestingActivities" name="IntercompanyInvestingActivities" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="debit" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_InventoriesTextualAbstract" name="InventoriesTextualAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_LeaseCostFinanceLeaseAbstract" name="LeaseCostFinanceLeaseAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_LesseeFinanceLeaseCashPaidForAmountsIncludedInMeasurementOfLeaseLiabilitiesAbstract" name="LesseeFinanceLeaseCashPaidForAmountsIncludedInMeasurementOfLeaseLiabilitiesAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_LesseeFinanceLeaseChangesInLeaseBalancesResultingFromNewandModifiedLeasesAbstract" name="LesseeFinanceLeaseChangesInLeaseBalancesResultingFromNewandModifiedLeasesAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_LesseeOperatingLaseChangesInLeaseBalancesResultingFromNewandModifiedLeasesAbstract" name="LesseeOperatingLaseChangesInLeaseBalancesResultingFromNewandModifiedLeasesAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_LesseeOperatingLeaseCashPaidForAmountsIncludedInMeasurementOfLeaseLiabilitiesAbstract" name="LesseeOperatingLeaseCashPaidForAmountsIncludedInMeasurementOfLeaseLiabilitiesAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_LesseeOtherSupplementalInformationAbstract" name="LesseeOtherSupplementalInformationAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_LesseeSupplementalCashFlowInformationAbstract" name="LesseeSupplementalCashFlowInformationAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_MVPTerminalMember" name="MVPTerminalMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_MVPTerminallingLLCMVPMember" name="MVPTerminallingLLCMVPMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_MagellanMidstreamPartnersLPMagellanMember" name="MagellanMidstreamPartnersLPMagellanMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_MinorAcquisitionsMember" name="MinorAcquisitionsMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_NoncurrentLeaseLiabilitiesReflectedInTheFollowingBalanceSheetLineItemsFinanceLeasesAbstract" name="NoncurrentLeaseLiabilitiesReflectedInTheFollowingBalanceSheetLineItemsFinanceLeasesAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_NoncurrentLeaseLiabilitiesReflectedInTheFollowingBalanceSheetLineItemsOperatingLeaseAbstract" name="NoncurrentLeaseLiabilitiesReflectedInTheFollowingBalanceSheetLineItemsOperatingLeaseAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element id="vlo_NumberOfEthanolPlantsOwnedByCompany" name="NumberOfEthanolPlantsOwnedByCompany" nillable="true" substitutionGroup="xbrli:item" type="xbrli:integerItemType" xbrli:periodType="instant" />
  <xsd:element id="vlo_NumberOfRefineriesOwnedByCompany" name="NumberOfRefineriesOwnedByCompany" nillable="true" substitutionGroup="xbrli:item" type="xbrli:integerItemType" xbrli:periodType="instant" />
  <xsd:element id="vlo_NumberOfRenewalOptions" name="NumberOfRenewalOptions" nillable="true" substitutionGroup="xbrli:item" type="xbrli:integerItemType" xbrli:periodType="instant" />
  <xsd:element abstract="true" id="vlo_OperatingLeaseAssetsAndLiabilitiesLesseeAbstract" name="OperatingLeaseAssetsAndLiabilitiesLesseeAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_OperatingLeaseCashFlowLesseeAbstract" name="OperatingLeaseCashFlowLesseeAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_OperatingLeaseLesseeOtherSupplementalInformationAbstract" name="OperatingLeaseLesseeOtherSupplementalInformationAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_OptionsHeldMaturityCurrentYearMember" name="OptionsHeldMaturityCurrentYearMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_OptionsHeldMaturityYearTwoMember" name="OptionsHeldMaturityYearTwoMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_OtherLetterOfCreditMember" name="OtherLetterOfCreditMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_OtherProductRevenuesMember" name="OtherProductRevenuesMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_OtherRevenuesMember" name="OtherRevenuesMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_OtherVariableInterestEntitiesMember" name="OtherVariableInterestEntitiesMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element id="vlo_PaymentsforCapitalImprovementsExcludingVariableInterestEntities" name="PaymentsforCapitalImprovementsExcludingVariableInterestEntities" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="credit" xbrli:periodType="duration" />
  <xsd:element id="vlo_PaymentsofOrdinaryDividendsNoncontrollingInterestandDistributionstoAffiliates" name="PaymentsofOrdinaryDividendsNoncontrollingInterestandDistributionstoAffiliates" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="credit" xbrli:periodType="duration" />
  <xsd:element id="vlo_PaymentstoAcquirePropertyPlantandEquipmentExcludingVariableInterestEntities" name="PaymentstoAcquirePropertyPlantandEquipmentExcludingVariableInterestEntities" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="credit" xbrli:periodType="duration" />
  <xsd:element id="vlo_PipelineCapacity" name="PipelineCapacity" nillable="true" substitutionGroup="xbrli:item" type="us-types:flowItemType" xbrli:periodType="instant" />
  <xsd:element abstract="true" id="vlo_PipelinesTerminalsandTanksMember" name="PipelinesTerminalsandTanksMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_PriceRiskManagementActivitiesTextualAbstract" name="PriceRiskManagementActivitiesTextualAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element id="vlo_ProceedsfromIssuanceofLongtermDebtExcludingVariableInterestEntities" name="ProceedsfromIssuanceofLongtermDebtExcludingVariableInterestEntities" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="debit" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_PureBiofuelsdelPeruS.A.C.Member" name="PureBiofuelsdelPeruS.A.C.Member" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_ROUAssetsNetReflectedInTheFollowingBalanceSheetLineItemsFinanceLeasesAbstract" name="ROUAssetsNetReflectedInTheFollowingBalanceSheetLineItemsFinanceLeasesAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_ROUAssetsNetReflectedInTheFollowingBalanceSheetLineItemsOperatingLeasesAbstract" name="ROUAssetsNetReflectedInTheFollowingBalanceSheetLineItemsOperatingLeasesAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_RefiningMember" name="RefiningMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element id="vlo_RenewableDieselFeedstocksandProducts" name="RenewableDieselFeedstocksandProducts" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="debit" xbrli:periodType="instant" />
  <xsd:element abstract="true" id="vlo_RenewableDieselMember" name="RenewableDieselMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_RenewableDieselProductMember" name="RenewableDieselProductMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element id="vlo_RepaymentsofDebtandLeaseObligationExcludingVariableInterestEntities" name="RepaymentsofDebtandLeaseObligationExcludingVariableInterestEntities" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="credit" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_ReportableSegmentTotalAssetsAbstract" name="ReportableSegmentTotalAssetsAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_SeniorNotesDueIn2020Member" name="SeniorNotesDueIn2020Member" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_SeniorNotesDueIn2029Member" name="SeniorNotesDueIn2029Member" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_SeniorNotesDueInMarch2019Member" name="SeniorNotesDueInMarch2019Member" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_SeniorNotesDuein2028Member" name="SeniorNotesDuein2028Member" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element id="vlo_TerminallingAgreementInitialTerm" name="TerminallingAgreementInitialTerm" nillable="true" substitutionGroup="xbrli:item" type="xbrli:durationItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_TradeAccountsReceivableContractswithCustomersMember" name="TradeAccountsReceivableContractswithCustomersMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_TransportationMarineMember" name="TransportationMarineMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_TransportationRailMember" name="TransportationRailMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element id="vlo_UndividedOwnershipInterestinAssetsPercentage" name="UndividedOwnershipInterestinAssetsPercentage" nillable="true" substitutionGroup="xbrli:item" type="num:percentItemType" xbrli:periodType="instant" />
  <xsd:element abstract="true" id="vlo_VLPRevolverMember" name="VLPRevolverMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_VLPSeniorNotesDueMarch2028Member" name="VLPSeniorNotesDueMarch2028Member" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_VLPSeniorNotesDuein2026Member" name="VLPSeniorNotesDuein2026Member" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_VLPSubordinatedNotesMemberMember" name="VLPSubordinatedNotesMemberMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_ValeroEnergyPartnersLPMember" name="ValeroEnergyPartnersLPMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_ValeroRevolverLetterofCreditMember" name="ValeroRevolverLetterofCreditMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_ValeroRevolverMember" name="ValeroRevolverMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element id="vlo_VariableInterestEntitiesConsolidatedPaymentsforCapitalImprovements" name="VariableInterestEntitiesConsolidatedPaymentsforCapitalImprovements" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="credit" xbrli:periodType="duration" />
  <xsd:element id="vlo_VariableInterestEntitiesConsolidatedPaymentstoAcquirePropertyPlantandEquipment" name="VariableInterestEntitiesConsolidatedPaymentstoAcquirePropertyPlantandEquipment" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="credit" xbrli:periodType="duration" />
  <xsd:element id="vlo_VariableInterestEntitiesConsolidatedProceedsfromIssuanceofLongtermDebt" name="VariableInterestEntitiesConsolidatedProceedsfromIssuanceofLongtermDebt" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="debit" xbrli:periodType="duration" />
  <xsd:element id="vlo_VariableInterestEntitiesConsolidatedRepaymentsofDebtandLeaseObligation" name="VariableInterestEntitiesConsolidatedRepaymentsofDebtandLeaseObligation" nillable="true" substitutionGroup="xbrli:item" type="xbrli:monetaryItemType" xbrli:balance="credit" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_VariableInterestEntityPrimaryBeneficiaryDiamondGreenDieselHoldingsLLCMember" name="VariableInterestEntityPrimaryBeneficiaryDiamondGreenDieselHoldingsLLCMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_VariableInterestEntityPrimaryBeneficiaryOtherVariableInterestEntitiesMember" name="VariableInterestEntityPrimaryBeneficiaryOtherVariableInterestEntitiesMember" nillable="true" substitutionGroup="xbrli:item" type="nonnum:domainItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_VariableInterestEntityTextualAbstract" name="VariableInterestEntityTextualAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
  <xsd:element abstract="true" id="vlo_VolumeofOutstandingContractsAbstract" name="VolumeofOutstandingContractsAbstract" nillable="true" substitutionGroup="xbrli:item" type="xbrli:stringItemType" xbrli:periodType="duration" />
</xsd:schema>
