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

    <schemaVersion>X0306</schemaVersion>

    <documentType>4</documentType>

    <periodOfReport>2017-03-03</periodOfReport>

    <notSubjectToSection16>0</notSubjectToSection16>

    <issuer>
        <issuerCik>0001379895</issuerCik>
        <issuerName>DYNEGY INC.</issuerName>
        <issuerTradingSymbol>DYN</issuerTradingSymbol>
    </issuer>

    <reportingOwner>
        <reportingOwnerId>
            <rptOwnerCik>0001236545</rptOwnerCik>
            <rptOwnerName>FLEXON ROBERT C</rptOwnerName>
        </reportingOwnerId>
        <reportingOwnerAddress>
            <rptOwnerStreet1>601 TRAVIS</rptOwnerStreet1>
            <rptOwnerStreet2>14TH FLOOR</rptOwnerStreet2>
            <rptOwnerCity>HOUSTON</rptOwnerCity>
            <rptOwnerState>TX</rptOwnerState>
            <rptOwnerZipCode>77002</rptOwnerZipCode>
            <rptOwnerStateDescription></rptOwnerStateDescription>
        </reportingOwnerAddress>
        <reportingOwnerRelationship>
            <isDirector>1</isDirector>
            <isOfficer>1</isOfficer>
            <isTenPercentOwner>0</isTenPercentOwner>
            <isOther>0</isOther>
            <officerTitle>President and CEO</officerTitle>
            <otherText></otherText>
        </reportingOwnerRelationship>
    </reportingOwner>

    <nonDerivativeTable>
        <nonDerivativeTransaction>
            <securityTitle>
                <value>Common Stock</value>
            </securityTitle>
            <transactionDate>
                <value>2017-03-03</value>
            </transactionDate>
            <deemedExecutionDate></deemedExecutionDate>
            <transactionCoding>
                <transactionFormType>4</transactionFormType>
                <transactionCode>F</transactionCode>
                <equitySwapInvolved>0</equitySwapInvolved>
                <footnoteId id="F1"/>
            </transactionCoding>
            <transactionAmounts>
                <transactionShares>
                    <value>10720</value>
                </transactionShares>
                <transactionPricePerShare>
                    <value>8.29</value>
                    <footnoteId id="F2"/>
                </transactionPricePerShare>
                <transactionAcquiredDisposedCode>
                    <value>D</value>
                </transactionAcquiredDisposedCode>
            </transactionAmounts>
            <postTransactionAmounts>
                <sharesOwnedFollowingTransaction>
                    <value>647072</value>
                    <footnoteId id="F3"/>
                </sharesOwnedFollowingTransaction>
            </postTransactionAmounts>
            <ownershipNature>
                <directOrIndirectOwnership>
                    <value>D</value>
                </directOrIndirectOwnership>
            </ownershipNature>
        </nonDerivativeTransaction>
    </nonDerivativeTable>

    <derivativeTable></derivativeTable>

    <footnotes>
        <footnote id="F1">These restricted stock units were withheld by Issuer to pay the taxes applicable to the vesting of 39,192 units of restricted stock on March 3, 2017.</footnote>
        <footnote id="F2">Reflects the closing stock price on March 3, 2017.</footnote>
        <footnote id="F3">Amount includes 20,087 restricted stock units that vest on March 3, 2018, 153,563 restricted stock units that vest on April 30, 2018 and 228,330 restricted stock units that vest in three annual equal installments beginning on March 1, 2018.</footnote>
    </footnotes>

    <ownerSignature>
        <signatureName>/s/ Heidi D. Lewis, Attorney-in-Fact</signatureName>
        <signatureDate>2017-03-07</signatureDate>
    </ownerSignature>
</ownershipDocument>
