The energy gain in microbes is driven by oxidizing an electron donor and reducing an electron acceptor. Variation in the electron acceptor conditions creates a feasibility to harness energy. In order to support the microbial respiration, electrons will transfer to the exocellular medium toward the available electron acceptor, especially in the absence of oxygen. The microbes can use a wide range of electron acceptors such as metals, nutrients, minerals, etc., including solid electrodes. When the microbes use the solid electrode as electron acceptors, the setup is called microbial fuel cell (MFC) and the electrons can be harvested and used for different applications. MFC can be defined as a microbially catalyzed electrochemical system which can facilitate the direct conversion of substrate to electricity through a cascade of redox reactions, especially in the absence of oxygen. Linking the microbial metabolism to anode and then transmitting the electrons to cathode generates a net electrical power from the degradation of available electron donor. This concept of MFC operation has expanded considerable interest in the recent research due to its application in the energy recovery from wastewater. Microbes in MFC can also use variety of organic or inorganic electron donors as well as acceptors to produce a surfeit of desirable biofuels or biochemicals which is termed as microbial electrosynthesis. Apart from the electrogensis, the applications of MFC are widespread in different fields including waste/wastewater remediation, toxic pollutants/xenobiotics removal, recovery of commercially viable products, sequestration of CO2, harvesting the energy stored in marine sediments, desalination, etc. In this chapter, an attempt was made to bring out all the existing applications of MFC into one platform to make a comprehensive understanding on the inherent potential of microbial metabolism, when the designated electron acceptor is present. © 2013 Springer-Verlag Berlin Heidelberg. All rights are reserved.