Incorporating　photocatalysis　into　benzylic　C(sp3)–H　oxidation　represents　a　recent　advance　of　organic　synthesis　in　a　sustainable　manner.　Although　photoinduced　charge　carriers　enable　the　C(sp3)–H　bond　to　be　activated　under　mild　conditions,　the　reaction　scale　and　activity　remain　hindered　by　the　photoactivation　efficiency.　Herein,　we　present　that　the　1.0%　V2O5@CN　photocatalyst,　a　visible-light-active　C3N4-based　material,　is　striking　active　for　the　aerobic　oxidation　of　benzylic　C(sp3)–H　bonds,　affording　a　conversion　rate　11.6　times　higher　than　that　of　independent　CN.　The　enhanced　activity　and　C(sp3)–H　bond　photoactivation,　as　well　as　the　induction　period　shortening　and　active　period　acceleration,　are　rationalized　by　the　low-EVB　hole　injection　from　V2O5　into　CN　and　the　boosted　charge　separation.　The　durability　and　utility　are　affirmed　in　multiple　catalytic　cycles,　scalable　long-term　reactions,　and　available　substrate　scopes.　Reactive　intermediate　studies　by　EPR　demonstrate　the　involvement　of　[rad]CH2Ph,　[rad]O2−,　and　[rad]OH　radicals　in　photoredox　catalysis.　The　mechanism　that　causes　the　change　of　main　product　species　is　attributed　to　the　formation　of　[rad]OH　in　the　later　reaction　stage.　This　work　indicates　a　unique　photoactive　V2O5@CN　catalysis　mode,　opening　up　the　efficient　use　of　CN　in　scalable　photocatalytic　toluene　oxidation.　©　2021　Elsevier　Inc.