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.　©　2023　Beijing　University　of　Technology.　All　rights　reserved.