Abstract: Bio-electro-Fenton (BEF) is a new technology by utilizing microbial fuel cells to drive electro-Fenton reaction, with a characteristic of simultaneous pollutant degradation and energy recovery, and has been employed in the treatment of diverse wastewaters. The dual-chamber BEF system has been extensively investigated. Firstly, this review outlined the principles and influencing factors of the dual-chamber BEF system. Subsequently, it summarized the application of the dual-chamber BEF system for treating high-concentration organic and refractory wastewater. Finally, it analyzed the main mechanisms involved in the dual-chamber BEF system and proposed future research directions. The results indicate that BEF, as a green, efficient, and sustainable technology, holds excellent application prospects. Future studies should focus on optimizing the system's pollutant treatment capacity, minimizing investment and operating costs, and broadening the application scope to realize the vision of using waste to treat waste.