Microbial electrolysis cells (MECs) have been explored for various applications, including the removal of industrial pollutants, wastewater treatment chemical synthesis, and biosensing. On the other hand, MEC technology is still in its early stages and faces significant obstacles regarding practical large-scale implementations. MECs are used for energy generation and hydrogen peroxide, methane, hydrogen/biohydrogen production, and pollutant removal. This review aimed to investigate the aforementioned uses in order to better understand the different applications of MECs in the following scenarios: MECs for energy generation and recycling, such as hydrogen, methane, and hydrogen peroxide; contaminant removal, particularly complex organic and inorganic contaminants; and resource recovery. MEC technology was examined in terms of new concepts, configuration optimization, electron transfer pathways in biocathodes, and coupling with other technologies for value-added applications, such as MEC anaerobic digestion, combined MEC–MFC, and others. The goal of the review was to help researchers and engineers understand the most recent developments in MEC technologies and applications.