The iron-catalyzed oxidation of arsenite (As(III)) associated with Fenton or Fenton-like reactions is one of the most efficient arsenic removal methods. However, the conventional chemical or electro-Fenton systems for the oxidation of As(III) are only efficient under acid conditions. In the present study, a cost-effective and efficient bio-electro-Fenton process was performed for As(III) oxidation in a dual-chamber microbial fuel cell (MFC) under neutral pH conditions. In such a system, the Fenton reagents, including H2O2 and Fe(II), were generated in situ by microbial-driven electro-reduction of O-2 and gamma-FeOOH, respectively, without an electricity supply. The results indicated that the process was capable of inducing As(III) oxidation with an apparent As(III) depletion first-order rate constant of 0.208 h(-1). The apparent oxidation current efficiency was calculated to be as high as 73.1%. The gamma-FeOOH dosage in the cathode was an important factor in determining the system performance. Fourier-transform infrared spectroscopy (FT-IR) analysis indicated that As(V) was bound to the solid surface as a surface complex but not as a precipitated solid phase. The mechanism of bio-E-Fenton reaction for As(III) oxidation was also proposed. The bio-electro-Fenton system makes it potentially attractive method for the detoxification of As(III) from aqueous solution. (C) 2014 Elsevier B.V. All rights reserved.