In this study, a microbial fuel cell (MFC)-biofilm electrode reactor (BER) coupled system was established for degradation of the azo dye Reactive Brilliant Red X-3B. In this system, electrical energy generated by the MFC degrades the azo dye in the BER without the need for an external power supply, and the effluent from the BER was used as the inflow for the MFC, with further degradation. The results indicated that the X-3B removal efficiency was 29.87% higher using this coupled system than in a control group. Moreover, a method was developed to prevent voltage reversal in stacked MFCs. Current was the key factor influencing removal efficiency in the BER. The X-3B degradation pathway and the types and transfer processes of intermediate products were further explored in our system coupled with gas chromatography-mass spectrometry. (C) 2016 Elsevier Ltd. All rights reserved.