The　indirect　anthraquinone　method　is　currently　used　to　produce　H2O2,　but　it　leads　to　high　energy　consumption　and　a　large　amount　of　chemical　waste.　Alternatively,　water　oxidation　reactions　offer　a　potential　green　approach　for　H2O2　production,　although　it　is　constrained　by　low　selectivity.　Herein,　the　functional　photoanodes　are　rationally　designed　for　H2O2　production　via　photocatalytic　water　oxidation.　Specifically,　P/Mo　co-doped　BiVO4　films　are　achieved　on　a　conductive　glass　to　serve　as　the　photocatalytic　layer,　which　is　coated　with　an　ultrathin　amorphous　TiO2　film　to　achieve　good　stability.　Importantly,　metal-free　P-doped　polymeric　carbon　nitride　dots　are　deposited　on　the　photoanode,　acting　as　the　reaction　centres.　This　innovative　approach　moves　away　from　the　traditional　reliance　on　inorganic　materials　as　co-catalysts　in　order　to　suppress　the　thermodynamically　favoured　O₂　evolution,　which,　in　turn,　significantly　enhances　the　selectivity,　efficiency　and　stability　of　H₂O₂　production.　Consequently,　an　optimal　selectivity　of　≈64%　for　H₂O₂　production　is　achieved　at　an　applied　voltage　bias　of　1.7 V　versus　RHE　in　a　1.0 m　KHCO3　solution,　achieving　a　yield　of　≈34.2 µmol　hr−1　cm−2.　This　research　offers　a　novel　strategy　for　developing　photocatalytic　films　with　optimised　co-catalysts　for　a　photoanode　in　photocatalytic　H2O2　synthesis.　©　2025　Wiley-VCH　GmbH.