The intensive use of triphenyltin chloride (TPTC) has caused serious environmental pollution. In this study, an effective method for TPTC degradation was proposed based on the Bio-Electron-Fenton process in microbial fuel cells (MFCs). The maximum voltage of the MFC with graphite felt as electrode was 278.47% higher than that of carbon cloth. The electricity generated by MFC can be used for in situ generation of H2O2 to a maximum of 135.96μmolL-1 at the Fe@Fe2O3(*)/graphite felt composite cathode, which further reacted with leached Fe2+ to produce hydroxyl radicals. While 100μmolL-1 TPTC was added to the cathodic chamber, the degradation efficiency of TPTC reached 78.32±2.07%, with a rate of 0.775±0.021μmolL-1h-1. This Bio-Electron-Fenton driving TPTC degradation might involve in SnC bonds breaking and the main process is probably a stepwise dephenylation until the formation of inorganic tin and CO2. This study provides an energy saving and efficient approach for TPTC degradation.