A coupled system consisting of a double-anode microbial fuel cell (MFC) unit and a biofilm electrode reactor (BER) has been applied to degrade the azo dye reactive brilliant red X-3B. In this system, the MFC effluent was used as the input of the BER. The MFC preliminarily degraded X-3B while generating electricity, and the BER obtained electrons from the MFC through the external circuit to continue degrading pollutants without the need for an external power supply. The X-3B removal efficiency was 41.93% higher in the coupled system than the control when the X-3B concentration was 3000 mg/L. The analysis of intermediate products showed that the azo bond of X-3B broke in the MFC, generating a large number of complex intermediates such as anthraquinones, which were further degraded into simple organic compounds in the BER. Meanwhile, the abundance of microbial taxa related to the degradation of refractory organics in the MFC was high, as was that of microbial taxa related to the degradation of simple organics in the BER. Furthermore, the abundance of microorganisms related to power generation in the MFC increased. These results provided an efficient strategy for improving electron utilization efficiency in the coupling system of bioelectrochemical system.