Developing electrolytic seawater catalysts with excellent performance is crucial for efficient hydrogen production. In this study, Ni2P nanoparticles anchored on NiMo oxides, denoted as NiMo-P, are synthesized through heat-induced aliquation and phosphating of Ni in the ammonium nickel molybdate. Physicochemical characterizations reveal that the abundant Ni2P nanoparticles are uniformly distributed on NiMo oxides. Electrochemical data reveal that a mere overpotential of 103 mV is sufficient to achieve −100 mA cm−2 in alkaline simulated seawater, which is significantly lower than that of Pt foil (179 mV) and commercial Pt/C (165 mV). This remarkable activity observed in NiMo-P may be due to the superior water dissociation activity and hydrogen desorption ability of the Ni2P nanoparticles, as calculated by density functional theory, which surpasses that of Pt. Meanwhile, the NiMo-P exhibits outstanding stability, as evidenced by the chronoamperometric curve. The current remains at 98.1% of its initial value after 500 h, which can be attributed to the etching-hydrolysis method that strengthens the catalyst-carrier interaction. Besides, the inherent repulsion toward chlorine ions at the cathode effectively avoids chemical corrosion. Importantly, when coupled with the previously reported anode, NiMo-P also exhibits exceptional performance in alkaline seawater.