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Abstract The broad employment of water electrolysis for hydrogen (H₂) production is restricted by its large voltage requirement and low energy conversion efficiency because of the sluggish oxygen evolution reaction (OER). Herein, we report a strategy to replace OER with a thermodynamically more favorable reaction, the partial oxidation of formaldehyde to formate under alkaline conditions, using a Cu₃Ag₇electrocatalyst. Such a strategy not only produces more valuable anodic product than O₂but also releases H₂at the anode with a small voltage input. Density functional theory studies indicate the H₂C(OH)O intermediate from formaldehyde hydration can be better stabilized on Cu₃Ag₇than on Cu or Ag, leading to a lower C-H cleavage barrier. A two-electrode electrolyzer employing an electrocatalyst of Cu₃Ag₇(+)||Ni₃N/Ni(–) can produce H₂at both anode and cathode simultaneously with an apparent 200% Faradaic efficiency, reaching a current density of 500 mA/cm²with a cell voltage of only 0.60 V.