An investigation was carried out aimed at checking the feasibility of the novel bio-electro-Fenton process with FeVO4/CF cathode on advanced treatment of coal gasification wastewater. The maximum power density arrived 849.7 mW/m(3) in MFC-FeVO4/CF system, which was corresponding to a current density of 2.6 A/m(3) at the voltage of 326.8 mV. The concentration of BOD5, COD, TOC and total phenols in the cathode effluent under short-circuit conditions were 4.5 mg/L, 32.5 mg/L, 8.8 mg/L and 15.6 mg/L, respectively, which all met the class -I criteria of the Integrated Wastewater Discharge Standard. FeVO4/CF could be employed as a two-way Fenton-like catalyst that leads to the production of more reactive oxygen species. The in situ generation of Fenton-like reagents (Fe(II, V(IV) and H2O2) at the cathode was demonstrated by the cyclic voltammetry measurement. This novel process provides a cost-effective alternative to extend the practical merits of traditional MFCs and Fenton towards advanced treatment of industrial wastewater.