Bioelectrochemical systems (BES) are novel hybrid systems which are designed to generate renewable energy from the low cost substrate in a sustainable way. Microbial fuel cells (MFCs) are the well studied application of BES systems that generate electricity from the wide variety of organic components and wastewaters. MFC mechanism deals with the microbial oxidation of organic molecules for the production of electrons and protons. The MFC design helps to build the electrochemical gradient on anode and cathode which leads for the bioelectricity generation. As whole reactions of MFCs happen at mild environmental and operating conditions and using waste organics as the substrate, it is defined as the sustainable and alternative option for global energy needs and attracted worldwide researchers into this research area. Apart from MFC, BES has other applications such as microbial electrolysis cells (MECs) for biohydrogen production, microbial desalinations cells (MDCs) for water desalination, and microbial electrosynthesis cells (MEC) for value added products formation. All these applications are designed to perform efficiently under mild operational conditions. Specific strains of bacteria or specifically enriched microbial consortia are acting as the biocatalyst for the oxidation and reduction of BES. Detailed function of the biocatalyst has been discussed in the other chapters of this book.