Microbial fuel cells (MFCs) are bio-electrochemical arrangements that utilises microbial uptake to generate electricity from wastewater. The effectiveness of MFC is directly influenced by the electrode materials. Conventional and innovative nanomaterial synthesised electrodes are all used in MFC, but the performance also varies based on those electrode materials. This study reviews all available literature based on the combination of nanomaterial-derived electrodes like carbon nanotubes, graphene, metal oxide nanoparticles and metal–organic frameworks to augment electron transfer and microbial union in MFCs. Comparison of physical characterisation, electrochemical performance, durability and bio-affinity of various nanomaterials are part of this chapter. This book chapter also aims to categorise ideal materials for real-world wastewater treatment and renewable energy generation. This work highlights the best possible nano-technetates electrodes for evolving effectual workable MFC system.