Electro-assisted Fenton-like (EAFL) system based on sulfate radicals (SO4-) has been extensively explored for the degradation of recalcitrant organic contaminant. Nevertheless, external power supply should be provided uninterruptedly in the EAFL process and thus the high energy consumption is ineluctable. Recently, microbial fuel cell (MFC), a bio-electrochemical system where exoelectricigens are used to catalyze fuels into electricity energy has gained popularity mainly due to its renewability. Herein, a novel heterogeneous EAFL system, hydronium jarosite (HJ) activation of peroxymonosulfate (PMS) in an electrochemical reactor driven by an uncoated single-chamber MFC (MFC/HJ/PMS), was employed to decolorize acid orange 7 (AO7). The results suggest that the MFC/HJ/PMS system can remove AO7 efficiently in a wide pH range (3-9). The concentration of total iron leached could meet European Union discharge standards and hydronium jarosite could be used at least three circles. The results of electron paramagnetic resonance analysis and radical scavenging experiments indicate SO4- is the major active species responsible for the AO7 elimination. The work provides an efficient, energy-saving and cost-effective approach to treat organic wastewater and develops the conceivable utilization of hydronium jarosite, precipitates produced in hydrometallurgical process.