In　the　design　of　photocatalysts　for　C(sp3)-H　selective　oxidation,　photogenerated　holes　have　been　regarded　as　critical　for　C(sp3)-H　dissociation.　However,　poor　charge-transfer　efficiency　restricts　the　localization　of　holes　on　the　surface　of　the　catalyst.　Herein,　a　Z-scheme　structure　modulated　by　interfacial　chemical　bonding　is　constructed　via　the　in　situ　growth　of　Cs3Bi2Br9　nanodots　(CBB)　on　defective　BiOBr　nanosheets　(d-BiOBr)　for　photocatalytic　toluene　selective　oxidation.　Benefited　from　the　interfacial　internal　electric　field,　the　Bi-Br　bond　becomes　a　direct　channel　to　accelerate　electron　transfer　from　the　conduction　band　of　d-BiOBr　to　the　valence　band　of　CBB,　resulting　in　a　higher　localization　of　charges　on　the　surface　of　CBB/d-BiOBr.　By　in　situ　diffuse　reflectance　infrared　Fourier　transform　spectroscopy,　electron　paramagnetic　resonance,　and　density　functional　theory　calculations,　the　surface　localization　of　holes　is　proved　to　be　essential　for　toluene　adsorption　and　the　dissociation　of　C(sp3)-H　bond.　The　optimized　CBB/d-BiOBr　performs　well　in　the　selective　oxidation　of　toluene　to　benzaldehyde　and　benzyl　alcohol,　giving　a　conversion　rate　of　up　to　72.3　mu　mol　h-1　and　a　selectivity　of　nearly　100%.　The　activity　of　CBB/d-BiOBr　is　26.6-fold　and　6.8-fold　that　of　pristine　d-BiOBr　and　CBB,　respectively.