Photocatalytic　oxidation　of　benzene　to　phenol　using　molecular　oxygen　(O2)　is　a　promising　alternative　to　the　traditional　cumene　process.　However,　the　selectivity　toward　phenol　is　often　poor　due　to　the　ring-opening　reaction　induced　by　the　superoxide　radical　(⋅O2−),　which　is　predominantly　produced　from　the　single-electron　reduction　of　O2.　Herein,　we　demonstrate　that　introducing　abundant　oxygen　vacancies　(OVs)　on　the　surface　of　titanium　dioxide　(TiO2)　facilitates　the　activation　of　O2　through　a　two-electron　reduction　process　instead　of　a　single-electron　reduction.　This　effectively　suppresses　the　generation　of　⋅O2−,　thereby　reducing　phenol　decomposition　and　significantly　enhancing　the　selectivity.　In　addition,　these　OVs　can　trap　the　electrons　to　promote　chare　separation　and　serve　as　the　adsorption　sites　for　O2　activation.　As　a　result,　the　introduction　of　abundant　OVs　on　the　surface　of　TiO2　not　only　enhances　phenol　yield　but　also　importantly　improves　selectivity　toward　phenol.　This　finding　enriches　our　understanding　of　how　OVs　influence　reaction　pathways　and　product　selectivity,　providing　valuable　insights　for　the　design　and　tailoring　of　OV-rich　photocatalysts　for　selective　organic　oxygenations.　©　2025　Wiley-VCH　GmbH.