Bipolar　hydrogen　production　(FOR//HER)　based　on　the　formaldehyde　oxidation　reaction　(FOR)　with　Cu-based　electrocatalysts　is　expected　to　replace　the　conventional　water　splitting　(OER//HER)　due　to　producing　H2　instead　of　O2　and　requiring　lower　energy.　However,　excessive　Cu+　formed　during　electrooxidation　can　influence　the　FOR　catalytic　activity.　Herein,　the　Cu/Cu2O/Co(OH)2　composite　electrocatalyst　is　successfully　synthesized　on　carbon　cloth　(CC)　by　two-step　electrodeposition.　The　as-synthesized　Cu/Cu2O/Co(OH)2/CC　shows　excellent　FOR　catalytic　performance　with　3.08　and　2.42　times　current　density　of　Cu/Cu2O/CC　at　0.1　and　0.5　VRHE,　respectively.　The　cell　voltage　required　to　supply　current　density　of　100　and　300　mA　cm−2　based　on　FOR//HER　of　Cu/Cu2O/Co(OH)2/CC(+)//Pt　sheet(−)　is　0.35　and　0.75　V,　respectively,　is　significantly　smaller　than　cell　voltage　of　OER//HER.　The　characterizations　and　DFT　calculations　indicate　that　the　electronic　regulation　at　the　composite　interface　promotes　the　transformation　of　the　formed　Cu+　to　Cu0,　which　ensures　sufficient　active　sites　and　provides　a　channel　for　the　rapid　transfer　of　electrons　during　FOR,　thus　accelerating　the　reaction　kinetics.　This　work　provides　a　new　idea　for　designing　catalysts　with　excellent　electrocatalytic　performance.　©　2025