The development of efficient urea oxidation reaction (UOR) catalysts helps UOR replace the oxygen evolution reaction (OER) in hydrogen production from water electrolysis. Here, we prepared Fe-doped Ni 2 P/NiSe 2 composite catalyst (Fe−Ni 2 P/NiSe 2 -12) by using phosphating-selenizating and acid etching to increase the intrinsic activity and active areas. Spectral characterization and theoretical calculations demonstrated that electrons flowed through the Ni−P−Fe−interface− Ni−Se−Fe, thus conferring high UOR activity to Fe−Ni 2 P/NiSe 2 -12, which only needed 1.39 V vs RHE to produce the current density of 100 mA cm −2 . Remarkably, this potential was 164 mV lower than that required for the OER under the same conditions. Furthermore, EIS demonstrated that UOR driven by the Fe−Ni 2 P/ NiSe 2 -12 exhibited faster interfacial reactions, charge transfer, and current response compared to OER. Consequently, the Fe−Ni 2 P/NiSe 2 -12 catalyst can effectively prevent competition with OER and NSOR, making it suitable for efficient hydrogen production in UOR-assisted water electrolysis. Notably, when water electrolysis is operated at a current density of 40 mA cm −2 , this UOR-assisted system can achieve a decrease of 140 mV in the potential compared to traditional water electrolysis. This study presents a novel strategy for UOR-assisted water splitting for energy-saving hydrogen production.