Direct　photocatalytic　conversion　of　benzene　to　phenol　with　molecular　oxygen　(O2)　is　a　green　alternative　to　the　traditional　synthesis.　The　key　is　to　find　an　effective　photocatalyst　to　do　the　trick.　Defect　engineering　of　semiconductors　with　oxygen　vacancies　(OVs)　is　an　emerging　strategy　for　catalyst　fabrication.　OVs　can　trap　electrons　to　promote　charge　separation　and　serving　as　adsorption　sites　for　O2　activation.　However,　the　randomly　distribution　of　OVs　on　the　semiconductor　surface　often　results　in　mismatching　the　charge　carrier　dynamics　under　irradiation,　thus　failing　to　fulfill　the　unique　advantages　of　OVs　for　photoredox　functions.　Herein,　we　demonstrate　that　abundant　OVs　can　be　facilely　generated　and　precisely　located　adjacent　to　the　reductive　sites　on　reducible　oxide　semiconductors　such　as　tungsten　oxide　(WO3)　via　a　simple　photochemistry　strategy.　Such　photoinduced　OVs　are　well　suited　for　photocatalytic　benzene　oxidation　with　O2　as　they　readily　capture　photogenerated　electrons　from　the　reductive　sites　of　WO3　to　activate　adsorbed　O2.　The　oxygen-isotope-labeling　experiments　further　confirm　that　the　OVs　also　facilitate　the　integration　of　oxygen　atoms　from　O2　into　phenol,　revealing　in　detail　the　pathway　for　photocatalytic　benzene　hydroxylation.　This　study　demonstrates　that　the　photochemistry　approach　is　an　appealing　strategy　for　the　synthesis　of　high-performance　OVs-rich　photocatalysts　for　solar-induced　chemical　conversion.　©　2024　Wiley-VCH　GmbH.