Enzyme-inspired by oxidative metabolism of cytochrome P450, the organic dye Acid Red 87 was introduced into metal-organic framework (MOF) PCN-222(Fe) by post-synthetic modification, to construct the heterogeneous enzyme-mimicking photocatalyst Acid Red 87@PCN-222(Fe) in which the proximal spatial distance between the dye and Fe-porphyrin moiety was expected to facilitate the photoinduced electron transfer for mimicking the electron transfer chain in P450. Employing 1-(4-methoxyphenyl)ethan-1-ol as the model substrate, the reaction conditions such as solvent, electronic sacrificial agent, oxygen source, and et al. were screened, and the optimized conditions were obtained, as shown below: sodium periodate as the oxygen source (53.5 mg, 0.25 mmol), 2,6-lutidine trifluoromethanesulfonate as the proton source (64.3 mg, 0.25 mmol), Acid Red 87@PCN-222(Fe) as the photocatalyst (12.0 mg, 0.00625 mmo), acetonitrile as the solvent (2 mL), under the photoirridation from 530-nm LED for 24 hours. The MOF-based photocatalyst could be recycled and reused for at least 3 times without remarkable deteriorations of catalytic reactivity and structural crystalline. This photocatalytic benzylic C—H oxidation was of broad substrate scope under the optimal conditions, and the highly regioselective benzylic oxidation of the nonsteroidal antiinflammatory drug, Pimeprofen®, at the C7-position, could be achieved in a yield of 48%. This protocol could be further expended to the oxidation of aryl thioethers to the corresponding aryl sulfoxides. Those results demonstrated the potential interests of this enzyme-inspired photocatalytic methodology in pharmaceutical field and industrial desulfurization.