Reductive decolorization of azo dye in wastewater was investigated in a dual-chamber microbial fuel cell (MFC) equipped with cathodes made of graphite or rutile-coated graphite. Rapid reduction of methyl orange (MO) with concomitant electricity production was achieved when the rutile-coated cathode was irradiated by visible light. The electrochemical impedance spectra (EIS) indicate that the polarization resistance ( R p) of the rutile-cathode MFC decreased from 1378 Ω in dark to 443.4 Ω in light, demonstrating that photocatalysis of rutile can enhance the cathodic electron transfer process. The combination of the biologically active anode and photocatalysis-supported cathodic reduction of MO obeyed the pseudo-first-order kinetics. The analysis of decolorization products indicates that the azo bond of MO was probably cleaved by photoelectrons at the irradiated rutile-cathode, resulting in the products of colorless hydrazine derivatives. In addition, concurrently enhanced electricity generation in the MFCs involving photocatalyzed cathodic reduction of MO was observed throughout this study.