Sustainable H2O2 supply and cost-effective elimination of residual H2O2 are two key challenges associated with the successful application of Fenton reaction for contaminant removal. In this study, an innovative Bioelectro-Fenton system capable of alternate switching between microbial electrolysis cell (MEC) and microbial fuel cell (MFC) mode of operation was developed to meet the challenges. In the MEC mode, a bioelectrochemical system (BES) produces H2O2 which reacts with Fenton's reagent (Fe II) to form hydroxyradical. The unused H2O2 (residual H2O2) is removed as electron acceptor by switching the system to MFC mode of operation. Complete decolorization and mineralization of 50 mg L-1 methylene blue (MB) was achieved in the MEC mode with apparent first order rate constants of 0.43 and 0.22 h(-1), respectively. After switching to the MFC mode, residual H2O2 of 180 mg L-1 was removed at a removal rate of 4.61 mg L-1 h(-1) while generating a maximum current density of 0.49 A m(-2). The MB degradation and residual H2O2 removal were affected by external resistance, cathode pH and initial MB concentration. Furthermore, the system performance was enhanced under stack operation. This study provides a proof-in-concept new system for efficient and cost-effective H2O2 control and recalcitrant pollutants removal. (C) 2015 Elsevier B.V. All rights reserved.