As the current depletion of fossil resources and global warming emerging, it is expected to establish sustainable production processes that circulate and utilize the resources available on the earth’s surface. In particular, there are expectations for the production of a value-added chemical from atmospheric carbon dioxide (CO2), however it is necessary to require a large amount of reducing power and energy. In recent studies, electrochemically active bacteria (EAB), microbes can be able to interact with a conductive material via extracellular electron transfer pathway, receive attention from application to bioelectrochemical systems such as microbial electrosynthesis system (MES). Since it is estimated that a value-added chemical production process combing EAB and solar cells can achieve an energy conversion efficiency higher than that of photosynthesis. In this report, we first describe EAB and subsequently summarize one of the attractive microbes, autotrophic acidophile iron-oxidizing bacteria and laboratory studies that have been conducted to towards development for a sustainable bioprocess using MES. We also discuss possibilities of MES biotechnology to utilize that facilitate the development of eco-friendly future industry.