Energy-saving　electrolytic　hydrogen　production　could　be　realized　by　replacing　sluggish　oxygen　evolution　reaction　(OER)　with　ethanol　oxidation　reaction　(EOR).　However,　it＇s　challenging　to　obtain　high-performance　electrocatalysts　with　excellent　activity　(close　to　the　theoretical　potential　for　EOR),　superior　production　selectivity,　and　stability　(anti-poisoning　during　EOR).　In　this　study,　a　C@Ni-Pd　bifunctional　catalyst　is　fabricated　towards　EOR　and　hydrogen　evolution　with　high　activity,　selectivity,　and　stability.　The　potential　of　EOR　over　the　C@Ni-Pd　catalyst　is　reduced　by　1.072　V　relative　to　OER　at　100　mA　cm−2.　In　the　water–ethanol　co-electrolysis　device,　the　onset　potential　is　as　low　as　0.4　V,　and　the　current　density　reaches　100　mA　cm−2　at　0.95　V.　The　power　consumption　of　device　is　still　lower　than　the　water　electrolysis　theory　at　high　current　density.　High-selective　acetate　could　be　co-produced　with　hydrogen　while　without　CO2　emission　over　C@Ni-Pd　bifunctional　catalysts.　DFT　and　in-situ　Raman　spectroscopy　results　indicate　that　the　highly-active　Pd　sites　endow　significant　energy-saving　hydrogen　production　effect.　The　high　selectivity　is　derived　from　the　abundant　OH*　on　the　surface　of　Ni,　which　promotes　the　conversion　of　*CH3CO　adsorbed　on　Pd　to　*CH3COOH.　This　study　provides　a　new　straight　to　design　high-performance　electrocatalysts　for　energy-saving　co-generation　of　pure　hydrogen　and　value-added　chemicals　from　organic　fuels　and　water　while　without　CO2　emissions.　©　2023　Elsevier　B.V.