In this study, we report on a photo-electrochemical/electro-Fenton oxidation (PEC/EF) system by coupling visible light driven photo-electrochemical oxidation (PEC) and electro-Fenton oxidation (EF) in an undivided cell. Bi2WO6 nanoplates deposited on FTO glass (Bi2WO6/FTO) and Fe@Fe2O3 core–shell nanowires supported on activated carbon fiber (Fe@Fe2O3/ACF) were used as the anode and the cathode in the PEC/EF system, respectively. This novel PEC/EF system showed much higher activity than the single PEC and EF systems on degradation of rhodamine B in aqueous solution at natural pH. Moreover, the degradation and the instantaneous current efficiencies of the PEC/EF system were increased by 154% and 26% in comparison with the sum of those of single PEC and EF systems, respectively. These significant enhancements could be attributed to the synergetic effect from better separation of photo-generated carriers in the photo-anode and the transfer of photo-electrons to the oxygen diffusion cathode to generate more electro-generated H2O2 and hydroxyl radicals on the Fenton cathode. The better separation of photo-generated carriers contribute more to the overall degradation enhancement than the photo-electrons generated H2O2 and the subsequent Fenton reaction on the cathode during the PEC/EF process.