At　present,　the　exploration　of　renewable　energy　is　a　huge　challenge,　and　water　electrolysis　is　regarded　as　a　promising　method　for　producing　hydrogen.　However,　the　hydrogen　evolution　reaction　(HER)　has　been　hampered　due　to　expensive　Pt-based　catalysts.　Herein,　the　Fe2P-coated　Ni2P/Co2P　nanospheres　with　yolk-shelled　structure　were　successfully　synthesized　according　to　a　facile　approach　of　doping　transition　metal　elements　and　phosphating　on　the　template　Ni-Co　nanospheres,　successively.　All　samples　were　tested　as　HER　catalysts　at　various　pH　environments.　The　results　showed　that　the　Fe2P-Ni2P/Co2P　possesses　superior　electrocatalytic　ability　and　good　stability.　The　Fe2P-Ni2P/Co2P　achieved　the　lower　ηonset　(overpotential　at　1.0　mA　cm−2)　of　36.6,　64.2,　and　65.9　mV,　η10　(overpotential　at　10　mA　cm−2)　of　89.7,　125,　and　212　mV,　and　Tafel　slopes　of　48.0,　60.3,　and　135　mV　dec−1　in　acidic,　alkaline,　and　neutral　solutions,　respectively,　exhibiting　an　excellent　electrocatalytic　activity　of　the　multicomponent　phosphides　for　HER.　©　2024　Hydrogen　Energy　Publications　LLC