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

    <schemaVersion>X0306</schemaVersion>

    <documentType>4</documentType>

    <periodOfReport>2017-11-03</periodOfReport>

    <notSubjectToSection16>0</notSubjectToSection16>

    <issuer>
        <issuerCik>0001167419</issuerCik>
        <issuerName>Riot Blockchain, Inc.</issuerName>
        <issuerTradingSymbol>RIOT</issuerTradingSymbol>
    </issuer>

    <reportingOwner>
        <reportingOwnerId>
            <rptOwnerCik>0001662216</rptOwnerCik>
            <rptOwnerName>Beeghley Michael Martin</rptOwnerName>
        </reportingOwnerId>
        <reportingOwnerAddress>
            <rptOwnerStreet1>C/O RIOT BLOCKCHAIN, INC.</rptOwnerStreet1>
            <rptOwnerStreet2>202 6TH STREET, SUITE 401</rptOwnerStreet2>
            <rptOwnerCity>CASTLE ROCK</rptOwnerCity>
            <rptOwnerState>CO</rptOwnerState>
            <rptOwnerZipCode>80104</rptOwnerZipCode>
            <rptOwnerStateDescription></rptOwnerStateDescription>
        </reportingOwnerAddress>
        <reportingOwnerRelationship>
            <isDirector>0</isDirector>
            <isOfficer>0</isOfficer>
            <isTenPercentOwner>0</isTenPercentOwner>
            <isOther>1</isOther>
            <officerTitle></officerTitle>
            <otherText>Former CEO, Chairman</otherText>
        </reportingOwnerRelationship>
    </reportingOwner>

    <nonDerivativeTable>
        <nonDerivativeTransaction>
            <securityTitle>
                <value>Common Stock</value>
            </securityTitle>
            <transactionDate>
                <value>2017-11-03</value>
            </transactionDate>
            <deemedExecutionDate></deemedExecutionDate>
            <transactionCoding>
                <transactionFormType>4</transactionFormType>
                <transactionCode>A</transactionCode>
                <equitySwapInvolved>0</equitySwapInvolved>
            </transactionCoding>
            <transactionAmounts>
                <transactionShares>
                    <value>40000</value>
                    <footnoteId id="F1"/>
                </transactionShares>
                <transactionPricePerShare>
                    <value>0.00</value>
                    <footnoteId id="F2"/>
                </transactionPricePerShare>
                <transactionAcquiredDisposedCode>
                    <value>A</value>
                </transactionAcquiredDisposedCode>
            </transactionAmounts>
            <postTransactionAmounts>
                <sharesOwnedFollowingTransaction>
                    <value>177918</value>
                    <footnoteId id="F3"/>
                </sharesOwnedFollowingTransaction>
            </postTransactionAmounts>
            <ownershipNature>
                <directOrIndirectOwnership>
                    <value>D</value>
                </directOrIndirectOwnership>
            </ownershipNature>
        </nonDerivativeTransaction>
    </nonDerivativeTable>

    <derivativeTable></derivativeTable>

    <footnotes>
        <footnote id="F1">Represents a restricted stock award under the Riot Blockchain, Inc. (f/k/a Bioptix, Inc.) Amended &amp; Restated Equity Incentive Plan (the &quot;Restricted Stock Award&quot;), which was awarded and immediately vested in connection with the Reporting Person's execution of a Separation Agreement.</footnote>
        <footnote id="F2">Restricted Stock Award is compensation for the Reporting Person's resignation as Chief Executive Officer of the Issuer.</footnote>
        <footnote id="F3">Represents shares vested or to be vested within 60 days pursuant to restricted stock awards.</footnote>
    </footnotes>

    <ownerSignature>
        <signatureName>/s/ Michael M. Beeghley</signatureName>
        <signatureDate>2017-11-07</signatureDate>
    </ownerSignature>
</ownershipDocument>
