Abstract In this new insight, the potential application of the eco-friendly bioanode material was investigated with the aim of ammonium removal and its recovery, alongside power generation from wastewater in bio-electrochemical systems (BESs). In this procedure, biodegradation of ammonia was directly accrued via bioanode compartment driven by in-situ generated bioelectricity. To this end, this protocol was implemented with the anaerobic microbial as a biocatalyst in an anode chamber, as well as aerobic cathode chamber and a Nafion117 membrane as a separator with attractive results for the BES. The findings of the study suggested that BES, at the optimum operational conditions, can be an effective process for removing the high concentrations of organic materials and ammonium from industrial wastewater. The maximum BES efficiency was obtained 94% for the ammonium removal with a chemical oxygen demand (COD) concentration of 10,000 mg/L and a maximum organic removal rate of 78% with a substrate concentration of 2000 mg/L. The maximum voltage, power and current density of the BES was 481 mV, 62.7 mW/m2, 570 mA/m2, respectively. Further, an increase in NH4Cl concentration improved the maximum current density (808 mA/m2). The results demonstrated that the bio-electrochemical system could be utilized to treat industrial wastewater, containing high amounts of ammonium and organic materials, by adjusting the organic matter to ammonium (COD/NH4+) ratio while simultaneously generating electricity. Generally, the application of this eco-design, and sustainable bioanode material can be a good foundation and new perspective for practical application with regards to green and sustainable chemistry.