Enhancing the activity of the cathode and reducing the voltage for electrochemical hydrodechlorination of chlorohydrocarbon were always the challenges in the area of electrochemical remediation. In this study, a novel cathode material of Ni-doped graphene generated by Ni nanoparticles dispersed evenly on graphene was prepared to electrochemically dechlorinate PCE in groundwater. The reduction potential of Ni-doped graphene for PCE electrochemical hydrodechlorination was -0.24 V ( Ag/AgCl) determined by cyclic voltammetry. A single MFC with a voltage of 0.389-0.460 V and a current of 0.221-0.257 mA could drive electrochemical hydrodechlorination of PCE effectively with Ni-doped graphene as the cathode catalyst, and the removal rate of PCE was significantly higher than that with single Ni or graphene as the cathode catalyst. Moreover, neutral conditions were more suitable for Ni-doped graphene to electrochemically hydrodechlorinate PCE in groundwater and no byproduct was accumulated.