In this study, a simple method of biocathode fabrication in a Cr(VI)-reducink microbial fuel cell (MFC) is demonstrated. A self-assembling graphene was decorated onto the biocathode microbially, constructing a graphene/biofilm, in situ. The maximum power density of the MFC with a graphene biocathode is 5.7 times that of the MFC with a graphite felt biocathode. Cr(VI) reduction was also enhanced, resulting in 100% removal of Cr(VI) within 48 h, at 40 mg/L Cr(VI), compared with only 58.3% removal of Cr(VI) in the MFC with a graphite felt biocathode. Cyclic voltammogram analyses showed that the graphene biocathode had faster electron transfer kinetics than the graphite felt version. Energy dispersive spectrometer (EDS) and X-ray photoelectron spectra (XPS) analysis revealed a possible adsorption-reduction mechanism for Cr(VI) reduction via the graphene biocathode. This study attempts to improve the efficiency of the biocathode in the Cr(VI)-reducing MFC, and provides a useful candidate method for the treatment of Cr(VI) contaminated wastewater, under neutral conditions. (C) 2016 Published by Elsevier B.V.