A heterostructure photocatalyst consisting of BiOCl nanoplates and a bismuth-organic hybrid layer (alias BiCl3Br-CTA) was synthesized through a one-step solvothermal process. The BiOCl/BiCl3Br-CTA heterostructures exhibited broad light absorption and enhanced electron-hole separation efficiency. Moreover, the abundant oxygen vacancies (OVs) and superoleophilic surface endowed the photocatalyst with high abilities for adsorption and activation of O-2 and toluene. Therefore, the BiOCl/BiCl3Br-CTA photocatalyst showed excellent activities for the C(sp(3))-H bond oxidation of toluene under full-spectrum irradiation and visible light of simulated sunlight, which are 6.8-fold and 237.8-fold, respectively, than those of BiOCl nanoplates. The photocatalytic mechanism was revealed by a series of controlled experiments and in situ ESR detections. The selective oxidation of toluene was promoted by the synergy between the electrons in BiOCl for activating O-2 and the holes in the BiCl3Br-CTA layer for activating the C(sp(3))-H bonds. This research demonstrates an effective strategy to construct high-activity photocatalysts for challenging organic transformations.