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

    <schemaVersion>X0206</schemaVersion>

    <documentType>3</documentType>

    <periodOfReport>2025-02-19</periodOfReport>

    <noSecuritiesOwned>1</noSecuritiesOwned>

    <issuer>
        <issuerCik>0001533040</issuerCik>
        <issuerName>Phio Pharmaceuticals Corp.</issuerName>
        <issuerTradingSymbol>PHIO</issuerTradingSymbol>
    </issuer>

    <reportingOwner>
        <reportingOwnerId>
            <rptOwnerCik>0001641063</rptOwnerCik>
            <rptOwnerName>Deming David H</rptOwnerName>
        </reportingOwnerId>
        <reportingOwnerAddress>
            <rptOwnerStreet1>C/O PHIO PHARMACEUTICALS CORP.</rptOwnerStreet1>
            <rptOwnerStreet2>11 APEX DR., SUITE 300A, PMB 2006</rptOwnerStreet2>
            <rptOwnerCity>MARLBOROUGH</rptOwnerCity>
            <rptOwnerState>MA</rptOwnerState>
            <rptOwnerZipCode>01752</rptOwnerZipCode>
            <rptOwnerStateDescription></rptOwnerStateDescription>
        </reportingOwnerAddress>
        <reportingOwnerRelationship>
            <isDirector>1</isDirector>
            <isOfficer>0</isOfficer>
            <isTenPercentOwner>0</isTenPercentOwner>
            <isOther>0</isOther>
        </reportingOwnerRelationship>
    </reportingOwner>

    <remarks>Exhibit 24 - Power of Attorney</remarks>

    <ownerSignature>
        <signatureName>/s/ Robert Bitterman attorney-in-fact for David H. Deming</signatureName>
        <signatureDate>2025-03-04</signatureDate>
    </ownerSignature>
</ownershipDocument>
