Solar-driven　organic　synthesis　using　halide　perovskites　(HPs)　has　garnered　much　attention,　but　their　unsatisfactory　conversion　efficiency　limits　further　applications.　Addressing　charge　dynamics　and　redox　site　issues　is　a　straightforward　approach　to　improving　performance.　Herein,　we　report　the　synergistic　charge　separation　and　active　site　modulation　in　lead-free　Cs3Bi2Br9　HP　using　N-vacancy　reticular　g-C3N4　nanosheet　for　selective　C(sp3)-H　bond　activation.　This　regulation　exhibits　a　strong　interfacial　interaction,　enabling　effective　charge　transfer　with　more　active　sites.　Theoretical　calculations　and　experimental　characterizations　detailed　enhanced　charge　separation　and　reduced　energy　barriers　for　surface　photoredox　reactions.　When　applied　to　toluene　oxidation　under　simulated　solar　light,　the　optimized　photocatalyst　achieves　a　total　conversion　rate　of　6865.3　μmol　g-1　h-1　and　an　outstanding　benzaldehyde　selectivity　of　over　92%,　outperforming　most　reported　HP-based　photocatalysts.　This　work　offers　a　universal　strategy　for　developing　efficient　HP　photocatalysts　for　solar-to-chemical　energy　conversion.　©　2025　American　Chemical　Society.