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

    <schemaVersion>X0206</schemaVersion>

    <documentType>3</documentType>

    <periodOfReport>2023-07-19</periodOfReport>

    <noSecuritiesOwned>1</noSecuritiesOwned>

    <issuer>
        <issuerCik>0001347858</issuerCik>
        <issuerName>22nd Century Group, Inc.</issuerName>
        <issuerTradingSymbol>XXII</issuerTradingSymbol>
    </issuer>

    <reportingOwner>
        <reportingOwnerId>
            <rptOwnerCik>0001472122</rptOwnerCik>
            <rptOwnerName>Arno Andrew</rptOwnerName>
        </reportingOwnerId>
        <reportingOwnerAddress>
            <rptOwnerStreet1>C/O 22ND CENTURY GROUP, INC.</rptOwnerStreet1>
            <rptOwnerStreet2>500 SENECA STREET, SUITE 507</rptOwnerStreet2>
            <rptOwnerCity>BUFFALO</rptOwnerCity>
            <rptOwnerState>NY</rptOwnerState>
            <rptOwnerZipCode>14204</rptOwnerZipCode>
            <rptOwnerStateDescription></rptOwnerStateDescription>
        </reportingOwnerAddress>
        <reportingOwnerRelationship>
            <isDirector>true</isDirector>
        </reportingOwnerRelationship>
    </reportingOwner>

    <ownerSignature>
        <signatureName>Andrew Arno by John J. Wolfel, as Attorney-in-Fact</signatureName>
        <signatureDate>2023-07-26</signatureDate>
    </ownerSignature>
</ownershipDocument>
