AbstractSince the early beginning, attention has been paid to the prospective application of two-dimensional (2D) graphene (Gr) nanomaterial applications due to its exceptional conductivity, huge surface area, and high mechanical strength. Microbial fuel cells (MFCs) are one of these vital potential applications. The restricted energy production of MFCs compared with other fuel cell technologies and expensive materials are the two major hindrances in its practical application. Gr is proposed for use in the MFC assembly to overcome such challenges either as an electrode or membrane material to increase the oxygen reduction reaction (ORR) efficiently. The synthesis procedure for Gr-based electrodes and membranes is complex, expensive, and energy-inefficient and contains harmful chemicals for a scaled-up application. Therefore, there is a further need for focused research into the design and synthesis of Gr-based electrodes and membrane materials. However, regardless of these challenges, Gr-based electrodes are a favorable alternative in MFCs’ assembly to attain sustainable wastewater treatment and electricity production. Considering these facts, the objective of this critical review is to assess the latest developments in the Gr applications in MFCs, aiming at Gr background, including properties, Gr synthesis, wastewater treatment, and power generation, which will help to understand the perception of Gr in MFC operation.