Graphene is an emerging material with superior physical and chemical properties, which can benefit the development of microbial fuel cells (MFC) in several aspects. Graphene-based anodes can enhance MFC performance with increased electron transfer efficiency, higher specific surface area and more active microbe-electrode-electrolyte interaction. For cathodic processes, oxygen reduction reaction is effectively catalyzed by graphene-based materials because of a favorable pathway and an increase in active sites and conductivity. Despite challenges, such as complexity in synthesis and property degeneration, graphene-based electrodes will be promising for developing MFCs and other bioelectrochemical systems to achieve sustainable water/wastewater treatment and bioenergy production.