Microbial electrosynthesis involves microorganisms that can convert electrical energy to chemical energy by its catalytic activity during reduction of carbon compounds. This technique, when combined with a microbial fuel cell, helps in treating wastewaters and in the generation of value-added chemicals without any production of harmful wastes. This book chapter briefly discusses different parameters that affect the rate of production of volatile fatty acids and how they can be improved. An economic analysis of the technology is briefly summarized. Scaling-up and intern-commercial implementation of microbial electrosynthesis is limited by the low rate of high-value chemical production and high cost of construction materials. Further research efforts are required to explain electron transfer mechanisms, gene modification of acetogens for long-chain acid production, and development of biocathodes using cheaper materials to lower the production cost of high-value chemicals. © 2021 Elsevier Inc. All rights reserved.