In the present study, the potential application of the bio-electro-Fenton (BEF) process for the treatment of medicinal herbs wastewater in a mediator-less microbial fuel cell (MFC) system is investigated. This process is operated in a dual-chamber MFC with anaerobic seed sludge as biocatalyst in an anode chamber under conditions of neutral pH, an aerobic cathode chamber equipped with a Fe@Fe2O3/graphite composite cathode and a Nafion membrane as a separator. The performance of the MFC is determined in three different mixed liquor suspended solids (MLSS) loadings, Nafions (112, 115) and a salt bridge in an air-cathode BEF process, in terms of power generation, chemical oxygen demand (COD) removal efficiency, columbic and energy efficiencies. Under optimal conditions, the batch experiment results show that the cathode chamber of the BEF reactor, equipped with Nafion 112 and inoculated with seed sludge at 3000 mg L(-1) MLSS concentration, produces the maximum power density of 49.76 mW m(-2), 0.56 mg L(-1) and 29 mol L(-1) of H2O2 and Fe(2+), respectively. Under these conditions, the MFC achieves COD removal 78.05% in the anaerobic anode chamber and 84.02% as a result of aerobic processes from the air-cathode BEF chamber, whilst the maximum voltage εcb and εE values are 600 mV, 4.09% and 1.37%, respectively.