Boosting photo-Fenton performance by enhancing mass transfer process of peroxy sulphate (PS) and inhibiting the recombination of photo-generation carriers is an appealing strategy. Herein, ZnO/BiOCl porous microsphere assembled by thin nanosheets was successfully fabricated via microwave-assistant method. The results discern that BOZ-30 can eliminate 75.2 % carbamazepine (CBZ, 2.5 mg L−1) in 180 min, which is 1.7 and 1.3 times folder than ZnO and BiOCl, respectively. Moreover, the catalytic mechanism revealed that 3D axial channels and interfacial oxygen vacancies (IOVs) enhance mass transfer process of PS, promote forming of BOZ-PS* complex, and boost the separation efficiency of photo-generated carriers. Therefore, myriad electrons are quickly arrived at surface active sites through thin nanosheets and trapped by BOZ-PS* composites, and then effectively transfer to CBZ. Eventually, PS was activated under the synergistic of IOVs and 3D axial channels. Furthermore, the structure-properties relationship of removal rate, specific area and total oxygen vacancies was established. This work shed a new light on to remove refractory pollution by the cooperation of defect engineering and morphology engineering.