A novel photocatalytic fuel cell system integrating electro-Fenton process comprised of WO3/W photoanode and Fe@Fe2O3/carbon felt cathode is constructed in an undivided chamber for pollutants degradation with simultaneous electricity production. Compared with single photocatalysis and electro-Fenton, the integration system achieves better organics removal efficiency. It is found that the increase of light intensity and electrolyte concentration could improve the performance, but too low or high pH value have a negative impact. The highest short circuit current density 0.59 mA/cm(2) and maximum power output 0.34 mW/cm(2) is obtained using 20 mg/L of methyl blue. Moreover, various indicators such as fill factor, coulombic efficiency, and cathodic H2O2 efficiency are analyzed. Furthermore, a reasonable working principle is proposed, indicating that the integration system performance is strengthened by better electron/hole separation and enhanced radical reactions. Therefore, the composite system is an excellent candidate for simultaneous wastewater treatment and energy generation.