Abstract Graphene, single layer of sp2 bonded carbon atoms, has gained immense scientific interest since its discovery in 2004. Its unique properties, viz., large surface area, excellent conductivity, high mechanical strength, high thermal stability, transparency, and flexibility, make it desirable for various applications such as sensing, energy storage, flexible electronic devices, touch screens, liquid crystal displays, photovoltaic cells, and organic light-emitting diodes, fuel cells, etc. In the recent past, graphene has been one of the most preferred electrode materials for microbial electrochemical technology (MET) owing to its higher specific surface area and increased electron transfer efficiency and biocompatibility, which are desirable properties for anodes particularly in microbial fuel cell (MFC). Graphene-based cathodes show higher catalytic activity for oxygen reduction reaction due to increased active sites, conductivity, and favorable pathway of reaction. In this context, this chapter reviews graphene's production methods, properties, and its applications in various areas, with a special focus on its application in MFCs.