An efficient and cost-effective bio-photo-electro-catalytic reactor (BPEC) was developed, it combined bio-anode with TiO2 photo-electro-catalytic air cathode and could remove rapidly model gas phase VOC ethyl acetate (EA) and generate electricity simultaneously. This BPEC system exhibited a synergistic effect between the photo-electro-catalysis and microbial fuel cell (MFC) bio-electrochemical process. Calculated kinetic constant of the BPEC system (0.085 min-1) was twice the sum of those of photocatalysis (only electrolyte in the anode, without microbes, 0.033 min-1) and MFC (no photocatalysis, 0.010 min-1) systems. Compared to BPEC with proton exchange membrane (PEM) separator (59.6 mW/cm2), the system with polyvinylidene fluoride (PVDF) membrane had a higher EA degradation rate and power generation (92.8 mW/cm2). A lower external resistance resulted in a faster EA degradation rate. This report provides a new platform for treating other kinds of gas pollutants via integrated bio-electrochemical and gas-solid photo-electro-catalytic reactions, with energy generation and conversions.