A novel self-driven photo-assisted fuel cell (PFC) system composed of a visible responsive photoanode (TiO2 nanotubes/Ag/AgBr) and polypyrrol/multi-walled carbon nanotube/Fe3O4 (Ppy/MWCNT/Fe3O4) cathode was constructed. A coupling method was employed by introducing CuFe-layered doubled hydroxide (CuFe-LDH) as a photoactivator of persulfate (PS) into a photo fuel cell (PFC) to promote the degradation of quinoline and generate synchronous electricity. The optimum PFC system indicated an efficient and stable removal of quinoline (98.2 ℅) with a rate constant of 1.69 min 1, an open circuit voltage of 1.1 V, a short circuit current of 2.85 mA cm 2, and a power density of 0.76 mW cm 2. The PFC/ CuFe-LDH/PS indicated significant cell performance, incrementing the quinoline degradation by 42.76% and electricity production by 80.26% compared to the single photocatalytic fuel cell system. This work presents a high-efficient approach to eliminate organic compounds and synchronously generate electric power.