Microbial fuel cells (MFCs) are sustainable energy technologies that could resolve pollution challenges brought by various activities. It can meet energy demand by producing bioelectricity through catabolizing organic matter. Over the past two decades, research on many microbes have been used in MFCs, which intrigued researchers to explore the underlying electron transfer mechanism between microbe and anode. Electron transfer between electrode and microorganism occurs via different pathways: direct, indirect electron transfer and interspecies electron transfer. Shewanella and Geobacter are well‐known for microbe–electrode and microbe–microbe electron transfer. This review provides an overview of the significant varieties of microbes utilized in MFCs for simultaneous bioelectricity generation and wastewater treatment. Mechanisms of different modes of electron transfer involved during the oxidation of organic wastes in the anode section of MFCs are highlighted. Furthermore, this review also details some of the techniques to promote extracellular electron transfer efficiency which is important for the enhanced performance of MFC in terms of power, current generation and wastewater remediation. A perspective of challenges to be addressed for the effective functioning of these technologies, opportunities for MFC systems to be scaled up and associated techno‐economic analysis are discussed. © 2024 Society of Chemical Industry (SCI).