A coupling system combining Fenton process with dual rotating disk photocatalytic fuel cell (PFC) was developed to improve methyl orange (MO) removal and simultaneous electricity production, in which the (NH4)(3)PO4 modified bamboo charcoal (BC) was acted as cathode catalyst. Due to the existence of the N and P containing functional groups on the BC catalyst and the rotating electrode, the hybrid system could efficiently reduce oxygen to generate some hydroxyl radical and related species for MO removal. Therefore, Fenton-PFC-BC with rotation system showed a superior MO removal efficiency of 85%, 2.4 times higher than that in the traditional Fenton-PFC-Pt with aeration system. The radicals inhibition assays and hydrogen peroxide quantitative studies revealed that HO center dot, h(+) and O-center dot(2)- were primarily responsible for MO degradation. Furthermore, the MO removal performance for Fenton-PFC-BC with rotation system was investigated at different parameters (such as rotating speed, BC loading, pH and ferrous ion concentration) to obtain optimal operation conditions. Results of energy analysis and reusability experiment showed that the proposed Fenton-PFC-BC with rotation system provided a cost-effective and stable method for the organic degradation and energy recovery.