Replacing oxygen evolution reaction (OER) by electrooxidations of organic compounds has been considered as a promising approach to enhance the energy conversion efficiency of the electrolytic water splitting proces. Developing efficient electrocatalysts with low potentials and high current densities is crucial for the large‐scale productions of H₂ and other value‐added chemicals. Herein, non‐noble metal electrocatalysts Co‐doped Ni₃S₂ self‐supported on a Ni foam (NF) substrate are prepared and used as catalysts for 5‐hydroxymethylfurfural (HMF) oxidation reaction (HMFOR) under alkaline aqueous conditions. For HMFOR, the Co_0.4NiS@NF electode achieves an extremely low onset potential of 0.9 V versus reversible hydrogen electrode (RHE) and records a large current density of 497 mA cm^–2 at 1.45 V versus RHE for HMFOR. During the HMFOR‐assisted H₂ production, the yield rates of 2,5‐furandicarboxylic acid (FDCA) and H₂ in a 10 mL electrolyte containing 10 × 10⁻³ M HMF are 330.4 µmol cm^–2 h^–1 and 1000 µmol cm^–2 h^–1, respectively. The Co_0.4NiS@NF electrocatalyst displays a good cycling durability toward HMFOR and can be used for the electrooxidation of other biomass‐derived chemicals. The findings present a facile route based on heteroatom doping to fabricate high‐performance catalyses that can facilitate the industrial‐level H₂ production by coupling the conventional HER cathodic processes with HMFOR.

Optimized electronic structures of Fe₃C/NC boosted NH₃production from nitrate electroreduction, which proceededviaa stepwise NO₃⁻–NO₂⁻–NH₃pathway.