Biomass is one of the most abundant renewable energy resources on the earth, which is also considered as one of the most promising alternatives to traditional fuel energy. In recent years, microbial fuel cell (MFC) which can directly convert the chemical energy from organic compounds into electric energy has been developed. By using MFC, biomass energy could be directly harvested with the form of electricity, the most convenient, wide-spread, and clean energy. Therefore, MFC was considered as another promising way to harness the sustainable energies in biomass and added new dimension to the biomass energy industry. In this review, the pretreatment methods for biomass towards electricity harvesting with MFC, and the microorganisms utilized in biomass-fueled MFC were summarized. Further, strategies for improving the performance of biomass-fueled MFC as well as future perspectives were highlighted.