The need for energy has increased dramatically in recent days. The development of alternative energy sources is alarmingly necessary due to the depletion of available fossil fuel resources, economic shifts, and the resulting environmental consequences. Biofuels are considered a promising and sustainable energy option because of their high efficiency, ease of production, and pollution-free operation. Microbial electrolysis cell (MEC) is emerging as a viable power generation approach that can be applied to the practical remediation of polluted water and hydrogen generation. MEC is a bio-electrochemical process that uses microbe-based catalysts to oxidize organic matter and inorganic materials, generating energy. In contrast, MEC is a reactor that involves electrolysis and a fuel cell to generate biohydrogen. It is the most efficient, environmentally benign, and cleanest method for making biohydrogen. The discussion begins with an overview of the fundamental process and thermodynamic principles involved in hydrogen generation. To gain deeper insights into the development of hydrogen production using MEC techniques, the review elaborates on influential factors affecting H2 production. These factors include microbial population, electrodes, membrane, and substrate. The analysis extends to examining current advancements in these elements. A succinct summary of recent developments in the MEC architectures inculcating operational factors (electrode, applied voltage, membrane, reactor design, etc.) that affect hydrogen production is further elaborated in this review. Finally, the article outlines the current scenarios in which MEC is employed and proposes practical pathways for scaling up MEC to overcome the existing constraints.