It　remains　challenges　to　efficiently　convert　carbon-based　fuels　such　as　methanol　from　CO2　into　electrical　energy　while　without　CO2　greenhouse　gas　emission.　Herein,　a　CO2-emission　free　direct　methanol　fuel　cell　(DMFC)　has　been　realized　through　using　unique　Pt-CoOOH/nickel　foam　anode　with　high　electro-catalytical　selectivity,　activity　and　stability.　The　DMFCs　demonstrate　simultaneous　production　of　18　mol　of　formate　for　every　1　kWh　of　electricity　output　with　peak　power　density　of　49.3　mW　cm−2　and　high　selectivity　of　formate　value-added　chemicals　up　to　96　%.　Moreover,　this　simple　procedure　does　not　consume　energy　while　output　electricity　compared　to　the　traditional　formate　production.　It　either　does　not　use　the　toxic　feedstock　of　CO　and　the　reaction　conditions　are　very　mild.　The　in-situ　Raman　test　indicates　that　CoOOH　acts　as　an　auxiliary　active　site　to　promote　the　conversion　of　*HCO　to　*HCOOH　and　improve　the　selectivity　of　formate.　In-situ　IR　tests　and　density　functional　theory　(DFT)　calculations　confirm　that　methanol　tends　to　be　oxidized　selectively　into　formate　rather　than　complete-oxidizing　into　CO2.　This　study　achieves　clean　and　efficient　utilization　of　carbon-based　fuels　to　co-generate　electrical　energy　and　value-added　chemicals　while　no　CO2　greenhouse　emission,　even　realize　the　＇negative　carbon＇　cycle.　©　2024　Elsevier　B.V.