Syngas, a mixture of carbon monoxide, hydrogen, and carbon dioxide, can be readily produced from a variety of feedstocks, including biomass, municipal solid waste, and industrial emissions. Anaerobic bacteria are conventionally used in fermentation process to convert organic substrates to desirable products. However, syngas fermentation can be challenging due the gaseous nature and poor solubility of syngas. Syngas electrofermentation combines biological conversion with electrochemical processes to enhance substrate utilization, product yield, and energy efficiency. Microorganisms, particularly acetogens and certain autotrophic bacteria, play an important role in syngas metabolism, converting carbon monoxide and hydrogen into acetate and other valuable products. Syngas electrofermentation is a sustainable method of converting gaseous carbon sources into useful products, including biofuels, biochemicals, and bioplastics, by combining microbial metabolism with electrochemical processes. Despite the immense potential of this process, there is a lack of detailed studies on this topic. The present chapter, therefore, aims to present an overview of the topic covering the concepts, applications, challenges, and scope of syngas electrofermentation technology.