Microbial electrosynthesis (MES) technology couples electrochemical reactions with microbial metabolism to generate organic molecules. MES technology offers a sustainable alternative to biochemical production by converting organic compounds and CO[[inf]]2[[/inf]] into value-added products such as organic acids, biogas, bioplastics, short-chain fatty acids (SCFAs), and alcohols. MES is a bioelectrochemical approach that enables the electron equivalents generating from the waste and wastewater for decarbonization and for valorization. Several factors such as the cathode, microorganisms, electrode materials, design, and membrane influence the productivity of the MES. At present, MES technology is at nascent stage, and the overall output from the process needs several folds of improvement for commercialization. This chapter discusses several aspects of MES technology along with valuable biochemical generation. The fundamental aspects of MES and the factors influencing the reactor performance are also discussed.