To explore the effect of different doping on the catalytic performance of nickel-based phosphides, four kinds of nickel-based precursors with different doped (Fe, Co, Mo, and W) nickel-based phosphides were first prepared by hydrothermal method, and then these precursors were phosphating by chemical vapor deposition method. The precursors showed large structural differences by SEM analysis. After phosphating, only NiMoP retained the similar morphology as that of its precursor and exhibited the best structural stability. XPS results indicated that the four different doped nickel-based phosphides showed different valence state structures, Fe and Co-doped nickel-based phosphides had similar low- valence electronic state structures, while Mo and W doped nickel-based phosphides had high-valence electronic state structures. Further electrochemical hydrogen evolution tests showed that the overpotential of NiMoP at a current density of 10 mA/cm2
was only 97 mV, which was similar to the 83 mV of the precious metal Pt, and much lower than the overpotential of the other three samples. At the same time, in the long-term stability test, NiMoP also showed better stability property than the other three phosphates, indicating its good catalytic activity of hydrogen evolution.