<?xml version="1.0"?>
<ownershipDocument>

    <schemaVersion>X0206</schemaVersion>

    <documentType>3</documentType>

    <periodOfReport>2012-09-27</periodOfReport>

    <noSecuritiesOwned>0</noSecuritiesOwned>

    <issuer>
        <issuerCik>0001099941</issuerCik>
        <issuerName>MVC CAPITAL, INC.</issuerName>
        <issuerTradingSymbol>MVC</issuerTradingSymbol>
    </issuer>

    <reportingOwner>
        <reportingOwnerId>
            <rptOwnerCik>0001067621</rptOwnerCik>
            <rptOwnerName>GOLDSTEIN PHILLIP</rptOwnerName>
        </reportingOwnerId>
        <reportingOwnerAddress>
            <rptOwnerStreet1>C/O MVC CAPITAL, INC.</rptOwnerStreet1>
            <rptOwnerStreet2>287 BOWMAN AVENUE, 2ND FLOOR</rptOwnerStreet2>
            <rptOwnerCity>PURCHASE</rptOwnerCity>
            <rptOwnerState>NY</rptOwnerState>
            <rptOwnerZipCode>10577</rptOwnerZipCode>
            <rptOwnerStateDescription></rptOwnerStateDescription>
        </reportingOwnerAddress>
        <reportingOwnerRelationship>
            <isDirector>1</isDirector>
            <isOfficer>0</isOfficer>
            <isTenPercentOwner>0</isTenPercentOwner>
            <isOther>0</isOther>
            <officerTitle></officerTitle>
            <otherText></otherText>
        </reportingOwnerRelationship>
    </reportingOwner>

    <nonDerivativeTable>
        <nonDerivativeHolding>
            <securityTitle>
                <value>Common Stock</value>
            </securityTitle>
            <postTransactionAmounts>
                <sharesOwnedFollowingTransaction>
                    <value>37250</value>
                </sharesOwnedFollowingTransaction>
            </postTransactionAmounts>
            <ownershipNature>
                <directOrIndirectOwnership>
                    <value>D</value>
                </directOrIndirectOwnership>
            </ownershipNature>
        </nonDerivativeHolding>
        <nonDerivativeHolding>
            <securityTitle>
                <value>Common Stock</value>
            </securityTitle>
            <postTransactionAmounts>
                <sharesOwnedFollowingTransaction>
                    <value>567422</value>
                </sharesOwnedFollowingTransaction>
            </postTransactionAmounts>
            <ownershipNature>
                <directOrIndirectOwnership>
                    <value>I</value>
                    <footnoteId id="F1"/>
                </directOrIndirectOwnership>
                <natureOfOwnership>
                    <value>See footnote</value>
                    <footnoteId id="F1"/>
                </natureOfOwnership>
            </ownershipNature>
        </nonDerivativeHolding>
    </nonDerivativeTable>

    <derivativeTable></derivativeTable>

    <footnotes>
        <footnote id="F1">These Shares are owned by private investment funds managed by Bulldog Investors.  Mr. Goldstein is a principal of Bulldog Investors.  Mr. Goldstein disclaims all beneficial ownership in these Shares to the extent such ownership exceeds Mr. Goldstein's pecuniary interest therein.</footnote>
    </footnotes>

    <remarks>The Reporting Person became a Director of the Issuer on September 27, 2012.</remarks>

    <ownerSignature>
        <signatureName>/s/ Phillip Goldstein</signatureName>
        <signatureDate>2012-10-02</signatureDate>
    </ownerSignature>
</ownershipDocument>
