The conversion of chemical energy contained in organic matter into electricity has become an object of interest for many scientists worldwide. This technology is used in microbial fuel cells (MFC). Apart from generating electrical energy, these cells can be used simultaneously for wastewater treatment. Although the technology is constantly being improved, currently functioning microbial fuel cells cannot provide appropriate output parameters to use on an industrial scale. One of the barriers is so-called extracellular electron transfer, which in turn depends on the electrode type used, its material, shape, and size. According to current literature, carbon, graphite, stainless steel, and ceramics are the most frequently used electrode materials. However, more and more often, scientists are turning to other, unusual materials, the production of which uses the newest technologies, and one of them is graphene. This material is modified in different ways and connected with other materials, and the results of this seem to be very promising. Scientists manage to get a higher level of extracellular electron transfer and, hence, higher output parameters of the whole system. This article describes chosen technologies and attempts made by scientists worldwide to use graphene in MFC and their results.