Over the last two decades, scientific communities have been more interested in turning organic waste materials into bioenergy. Microbial fuel cells (MFC) can degrade organic wastewater and produce electrical power. Many constraints have limited the development of MFC. Among them, the anode biofilm development is one of the significant constraints that need to be improved. This review delineates the role of various biological components in the development of electroactive biofilm. The current article focuses on the numerous electron exchange methods for microbiome-induced electron transfer activity, the different proteins, and secretory chemicals involved in electron transfer. This study also focuses on several proteomics and genomics methodologies that have been adopted and developed to improve the extra electron transfer mechanism in electroactive bacteria. Recent advances and publications on synthetic biology and genetic engineering in investigating the direct and indirect electron transport phenomena have also been highlighted. This review helps the reader to understand the recent development in the genetic manipulations of the biofilm, electrode material modifications, EET mechanisms, and operational strategies for improving anode performance. This review also discusses the challenges in present technology and the future direction for improving biofilm production at the anode.