H2O2　as　an　essential　chemical　can　be　produced　by　photoanodic　water　oxidation　reaction　but　is　restricted　by　low　production　rate　and　poor　selectivity.　Herein,　three　kinds　of　transition　metal　phosphide,　namely　Fe2P,　Co2P,　and　Ni5P4,　have　been　loaded　on　Mo　doped　BiVO4　(MB)　photoanodes　to　promote　H2O2　production.　Among　them,　the　optimal　performance　has　been　achieved　by　Ni5P4/MB　photoanode　with　the　yield　of　20.8　µmol　h−1　cm−2　and　the　selectivity　of　41.9　%　at　the　applied　voltage　of　1.7　V　(vs.　RHE)　under　AM　1.5　G　illumination.　By　loading　Ni5P4　on　MB,　the　production　rate　of　OH•　radicals　and　the　desorption　of　the　as-formed　H2O2　have　been　promoted.　The　intermediates,　OH•　radicals,　have　been　in-situ　applied　for　tetracycline　degradation,　and　Ni5P4/MB　photoanode　presents　the　best　performance.　This　work　has　demonstrated　the　developments　of　metal　phosphide　as　co-catalysts　for　photoanodic　H2O2　production　from　water　and　meanwhile　paved　the　pathway　for　its　in-situ　use　in　water　disinfectant.　©　2023