<p>The increasing release of complex, recalcitrant pollutants from industrial and municipal activities into global water systems necessitates advanced treatment solutions beyond conventional methods. The Bio-Electro-Fenton (BEF) process offers a sustainable alternative by integrating microbial metabolism with electrochemically driven advanced oxidation for the degradation of persistent organic contaminants. This review synthesizes fragmented, cross-disciplinary research to provide a coherent overview of BEF technology, unifying current understanding of its fundamental mechanisms and practical applications. It discusses key bio-electrochemical pathways governing hydrogen peroxide generation and hydroxyl radical formation, recent advances in electrode materials and cathode composites, and the influence of reactor configurations and operating parameters on treatment performance. Reported studies demonstrate high removal efficiencies for a wide range of recalcitrant pollutants, with reduced chemical input, limited sludge production, and the potential for low or near energy-neutral operation under optimized conditions. At the same time, challenges related to reactor scale-up, long hydraulic retention times for certain compounds, material costs, and process control remain significant barriers to large-scale implementation. By consolidating current knowledge and identifying realistic opportunities and limitations, this review provides a critical reference to support the continued development of BEF systems toward practical wastewater treatment applications.</p> Graphical Abstract <p></p>