Sustainable energy sources are technologies that use renewable resources to generate energy and in today’s time require dire attention, and bioelectrochemical systems (BESs) are one of the many such technologies. As non-renewable resources are depleting day by day, harnessing nature’s potential in technological advancements is key to addressing climate and environmental challenges. BESs acquire microbial potential, specifically electroactive bacteria (EAB) for their metabolic activity utilizing organic matter and pollutants from wastes, and in turn generate and extracellularly release electrons, which are captured through a conductive material, thus producing bioelectricity. Industrial wastes alone majorly account for the release of complex recalcitrant pollutants and organic matter in the environment, including heavy metals, dye compounds, fine chemicals, pharmaceuticals and hydrocarbons. Conventional techniques (ion exchange, adsorption, advanced oxidation and filtration) are costly, energy intensive and insufficient to completely remove or act against emerging recalcitrant pollutants. Advanced sustainable technologies like BESs that can be incorporated into hybrid technologies can enhance the efficiency of the systems and achieve the maximum possible pollutant removal. Various systems that come under BESs like microbial desalination cells (MDCs), microbial fuel cells (MFCs), microbial electrolysis cells (MECs) and microbial electrosynthesis (MES) cells are used in the generation of bioelectricity, production of valuable products and the desalination of water, along with simultaneous treatment of wastewater. Thus, the development of these systems through efficient design and the use of novel materials and bacterial strains with enhanced potential for bioremediation and bioelectricity production is essential.