Emissions of volatile organic compounds (VOCs) air pollutants could worsen air quality and adversely affect human health, thus developing more efficient low-temperature VOCs removal techniques is desired. A novel continuous system integrating UV-assisted photo-electrochemical catalysis with microbial fuel cell (UV-assisted PEC-MFC) has been established for promoting removal of gaseous ethyl acetate or toluene and generating electricity simultaneously. In this system, CeO2/TiO2/ACF catalytic cathode is prepared and used for combination with bio-anode for accelerating cathodic reaction. This UV-assisted PEC-MFC system exhibits an excellent elimination capacity (EC) of ethyl acetate (∼0.39 g/m3, EC: ∼2.52 g/m3/h) or toluene (∼0.29 g/m3, EC: 1.89 g/m3/h) under close-circuit condition. Furthermore, an outstanding elimination capacity (EC: 28.04 g/m3/h) for high concentration toluene (∼4.10 g/m3) removal is obtained after toluene gas passes sequentially through the catalytic cathode then the bio-anode. This way of PEC degradation and biodegradation, avoids inhibition of exoelectrogens activity from toxicity of high concentration toluene. Simultaneously, the cell voltage of UV-assisted PEC-MFC system is stable at 0.11 V (vs. SCE) and 1.452×10-4 kWh is generated from treatment of toluene gas stream in 6 h duration time. The possible mechanism of VOCs removal in this novel system has been proposed and discussed. This study provides new technical basis for treating gaseous pollutants via integrating photo-electrochemical catalysis with electricity generating microbial fuel cell for energy conversion.