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

    <schemaVersion>X0306</schemaVersion>

    <documentType>4</documentType>

    <periodOfReport>2018-03-21</periodOfReport>

    <notSubjectToSection16>0</notSubjectToSection16>

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

    <reportingOwner>
        <reportingOwnerId>
            <rptOwnerCik>0001721702</rptOwnerCik>
            <rptOwnerName>Les Jason</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>1</isDirector>
            <isOfficer>0</isOfficer>
            <isTenPercentOwner>0</isTenPercentOwner>
            <isOther>0</isOther>
            <officerTitle></officerTitle>
            <otherText></otherText>
        </reportingOwnerRelationship>
    </reportingOwner>

    <nonDerivativeTable>
        <nonDerivativeTransaction>
            <securityTitle>
                <value>Common Stock</value>
            </securityTitle>
            <transactionDate>
                <value>2018-03-21</value>
            </transactionDate>
            <deemedExecutionDate></deemedExecutionDate>
            <transactionCoding>
                <transactionFormType>4</transactionFormType>
                <transactionCode>A</transactionCode>
                <equitySwapInvolved>0</equitySwapInvolved>
            </transactionCoding>
            <transactionAmounts>
                <transactionShares>
                    <value>7500</value>
                    <footnoteId id="F1"/>
                </transactionShares>
                <transactionPricePerShare>
                    <value>0.00</value>
                    <footnoteId id="F1"/>
                </transactionPricePerShare>
                <transactionAcquiredDisposedCode>
                    <value>A</value>
                </transactionAcquiredDisposedCode>
            </transactionAmounts>
            <postTransactionAmounts>
                <sharesOwnedFollowingTransaction>
                    <value>30000</value>
                    <footnoteId id="F2"/>
                </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 shall vest in 6 equal monthly installments, beginning on the one month anniversary of the date of issuance.</footnote>
        <footnote id="F2">Includes restricted stock award of 7,500 shares made on November 3, 2017 in connection with the Reporting Person's appointment as a Director of the Issuer, which shall vest in 24 equal monthly installments over a two year period, beginning on the one month anniversary of the date of issuance. Also includes 15,000 shares issued in connection with the Reporting Person serving on the Issuer's Advisory Board.</footnote>
    </footnotes>

    <ownerSignature>
        <signatureName>/s/ Jason Les</signatureName>
        <signatureDate>2018-03-23</signatureDate>
    </ownerSignature>
</ownershipDocument>
