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

    <schemaVersion>X0206</schemaVersion>

    <documentType>3</documentType>

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

    <noSecuritiesOwned>0</noSecuritiesOwned>

    <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>
        <nonDerivativeHolding>
            <securityTitle>
                <value>Common Stock</value>
            </securityTitle>
            <postTransactionAmounts>
                <sharesOwnedFollowingTransaction>
                    <value>7500</value>
                    <footnoteId id="F1"/>
                </sharesOwnedFollowingTransaction>
            </postTransactionAmounts>
            <ownershipNature>
                <directOrIndirectOwnership>
                    <value>D</value>
                </directOrIndirectOwnership>
            </ownershipNature>
        </nonDerivativeHolding>
    </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 granted 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, subject to the reporting person's continued service with the Issuer on each respective vesting date. If, during the vesting period a Qualified Transaction occurs, as defined in the February 3, 2017 Board of Director minutes, the grant shall vest fully.</footnote>
    </footnotes>

    <ownerSignature>
        <signatureName>/s/ Jason Les</signatureName>
        <signatureDate>2017-11-08</signatureDate>
    </ownerSignature>
</ownershipDocument>
