Photocatalytic　water　splitting　by　semiconductors　is　a　promising　technology　to　produce　clean　H2　fuel,　but　the　efficiency　is　restrained　seriously　by　the　high　overpotential　of　the　H2-evolution　reaction　together　with　the　high　recombination　rate　of　photoinduced　charges.　To　enhance　H2　production,　it　is　highly　desirable　yet　challenging　to　explore　an　efficient　reductive　cocatalyst　and　place　it　precisely　on　the　right　sites　of　the　photocatalyst　surface　to　work　the　proton　reduction　reaction　exclusively.　Herein,　the　metalloid　NixP　cocatalyst　is　exactly　positioned　on　the　Z-scheme　Cd0.5Zn0.5S/NiTiO3　(CZS/NTO)　heterostructure　through　a　facile　photodeposition　strategy,　which　renders　the　cocatalyst　form　solely　at　the　electron-collecting　locations.　It　is　revealed　that　the　directional　transfer　of　photoexcited　electrons　from　Cd0.5Zn0.5S　to　NixP　suppresses　the　quenching　of　charge　carriers.　Under　visible　light,　the　CZS/NTO　hybrid　loaded　with　the　NixP　cocatalyst　exhibits　an　optimal　H2　yield　rate　of　1103　μmol　h−1　(i.e.,　27.57　mmol　h−1　g−1),　which　is　about　twofold　of　pristine　CZS/NTO　and　comparable　to　the　counterpart　deposited　with　the　Pt　cocatalyst.　Besides,　the　high　apparent　quantum　yield　(AQY)　of　56%　is　reached　at　400　nm.　Further,　the　mechanisms　of　the　cocatalyst　formation　and　the　H2　generation　reaction　are　discussed　in　detail.　©　2023　The　Authors