Advanced　oxidation　processes　utilizing　hydrogen　peroxide　(H2O2)　are　widely　employed　for　the　treatment　of　organic　pollutions.　However,　the　conventional　anthraquinone　method　for　H2O2　synthesis　is　unsuitable　for　this　application　owing　to　its　hazardous　and　costly　nature.　Alternative　approaches　involve　a　photoelectrochemical　method.　Herein,　tungsten　trioxide　(WO3)　photoanode　has　been　used　for　the　conversion　of　H2O　into　H2O2　through　oxidation　reaction　from　a　PEC　system,　simultaneously　utilizing　in-situ　generated　hydroxyl　(OH•)　radicals　for　tetracycline　degradation.　By　manipulating　the　ratio　of　crystal　facets　between　(0　2　0)　and　(2　0　0)　of　the　WO3　photoanode,　a　significant　improvement　in　H2O2　production　has　been　achieved　by　increasing　the　proportion　of　(0　2　0)　facet.　The　production　rate　of　WO3　photoanode　enriched　with　the　(0　2　0)　facet　is　approximately　1.9　times　higher　than　that　enriched　with　(2　0　0)　facet.　This　enhanced　H2O2　production　performance　can　be　attributed　to　the　improved　formation　of　OH•　radicals　and　the　accelerated　desorption　of　H2O2　on　the　(0　2　0)　facet.　Simultaneously,　the　in-situ　generated　OH•　radicals　are　applied　for　tetracycline　degradation.　Under　illumination　of　sunlight　stimulator　for　180　min,　the　optimal　photoanode　achieves　a　degradation　rate　of　86.7%　for　tetracycline.　Furthermore,　the　resulting　chemicals　have　been　analyzed,　revealing　that　C8H10O　and　C7H8O　were　formed　as　the　primary　products.　Notably,　these　products　exhibit　significantly　lower　toxicity　compared　to　tetracycline.　This　study　presents　a　promising　approach　for　the　rational　design　of　WO3　based　photoanodes　for　oxidation　reaction,　including　not　only　H2O2　production　but　also　the　efficient　degradation　of　organic　pollutants.　©　2023　Elsevier　Inc.