With the growing population, the demand for electricity and waste generation is increasing exponentially, causing an alarming situation and threat to the environment. Recently, the production of bioelectricity from waste materials has emerged as a sustainable and innovative approach that subsequently provides solutions to both environmental and energy generation demands. This chapter deliberates the challenges and advancements in mobilizing bioelectricity generated by microbial fuel cells (MFCs) by undergoing numerous bioconversion technologies like anaerobic digestion of waste organic material. However, the recent advancements in reactor design, microbial consortia optimization, and electrode materials have significantly contributed to bioelectricity generation’s scalability and efficiency. Further, the amalgamation of bioengineering and nanotechnology significantly intensified the electron transfer rates and overall performance of the system. Despite this, the numerous provocations like operational stability, large-scale implementation, and economic viability remain due to waste heterogeneity, low power output, and maintenance of bio-electrochemical systems. Herein this chapter, the innovative solutions, potential environmental and economic benefits, and the latest research trends are discussed, with an emphasis on the future research directions aiming to achieve sustainable energy production while overcoming the technical barriers at the industrial scale.