Converting　carbon-based　molecular　fuels　into　electricity　efficiently　and　cleanly　without　emitting　CO2　remains　a　challenge.　Conventional　fuel　cells　using　noble　metals　as　anode　catalysts　often　suffer　performance　degradation　due　to　CO　poisoning　and　a　host　of　problems　associated　with　CO2　production.　This　study　provides　a　CO2-emission-free　direct　formaldehyde　fuel　cell.　It　enables　a　flow　of　electricity　while　producing　H2　and　valuable　formate.　Unlike　conventional　carbon-based　molecules　electrooxidation,　formaldehyde　1-electron　oxidation　is　performed　on　the　Cu　anode　with　high　selectivity,　thus　generating　formate　and　H2　without　undergoing　CO2　pathway.　In　addition,　the　fuel　cell　produces　0.62　Nm3　H2　and　53　mol　formate　per　1　kWh　of　electricity　generated,　with　an　open　circuit　voltage　of　up　to　1　V　and　a　peak　power　density　of　350　mW　cm−2.　This　study　puts　forward　a　zero-carbon　solution　for　the　efficient　utilization　of　carbon-based　molecule　fuels　that　generates　electricity,　hydrogen　and　valuable　chemicals　in　synchronization.　©　2023　Wiley-VCH　GmbH.