Incorporating　photocatalysis　into　benzylic　C(sp(3))-H　oxidation　represents　a　recent　advance　of　organic　synthesis　in　a　sustainable　manner.　Although　photoinduced　charge　carriers　enable　the　C(sp(3))-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(sp(3))-H　bonds,　affording　a　conversion　rate　11.6　times　higher　than　that　of　independent　CN.　The　enhanced　activity　and　C(sp(3))-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　(CH2Ph)-C-center　dot,　O-center　dot(2),　and　(OH)-O-center　dot　radicals　in　photoredox　catalysis.　The　mechanism　that　causes　the　change　of　main　product　species　is　attributed　to　the　formation　of　(OH)-O-center　dot　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.　(C)　2021　Elsevier　Inc.　All　rights　reserved.