A hierarchically photocatalytic microbial fuel cell system (PMFC) coupled with TiO2 photoanode and bioanode was established to enhance the power generation based on single-chamber MFC. Compared with the conventional anaerobic mode, oxygen in the solution could be utilized by the photoanode of PMFC to improve the removal of o-chlorophenol (2-CP). The maximum power densities were increasing from 261 (MFC) to 301 mW/m2 (PMFC). The removal efficiency of 2-CP (5 mg/L) in PMFC was 76.20% and higher than that in MFC (19.33%) and by photocatalysis (49.23%). The electron-hole separation efficiencies were decreasing with the increasing of dissolved oxygen, causing a low efficiency of photocatalysis, due to the reduction of the current density of the systems. The abundance of Geobacter sp., PHOS-HE36 fam., and Pseudomonas sp. was increased with illumination, contributing to improve the electricity production and 2-CP degradation. The only detective intermediate of 1,2-dichlorobenzene in PMFC indicated that the microbes could regulate the degradation pathway of 2-CP in the coupling system. These findings provided an feasible method for the effective degradation of refractory organic compounds and simultaneous energy recovery by combining photocatalysis and microbial power generation.