The intensified burning of fossil fuels and the discharging of industrial wastes are severe threats to the environment. The released CO₂ and organic fractions of industrial and municipal wastes exacerbate global warming. Converting the released CO₂ and organic wastes into beneficial electricity and biofuel-chemicals is deemed an environmental necessity. Microbial electrosynthesis (MES) presents a promising technology for bio-electrochemical conversion of released CO₂ and organic wastes into electricity and biofuel-chemicals using external-powered and/or self-powered microbial oxidation/reduction processes. The MES system consists of anodic and cathodic processes. The technology mostly relies on the capacity of electron transfer from electroactive biofilm to the electrode for reducing organics into value-added chemicals and sustaining their respiration and growth. The current review aims to summarize and explore the diversified application of electrogenic microbes and their metabolic pathways of electron transfer. It also summarizes the MES reactor design and operational parameters that influence the catalysis of biofilm and hence, the system performance. The review concludes with a critical evaluation of technical challenges that should be overcome before large-scale implementation. Furthermore, various recommendations on technical perspectives for successful implementation and application, including future research directions, are presented in this study.