Microbial fuel cell (MFC) is a promising approach that could utilize microorganisms to oxidize biodegradable pollutants in wastewater and generate electrical power simultaneously. Introducing advanced anode nanomaterials is generally considered as an effective way to enhance MFC performance by increasing bacterial adhesion and facilitating extracellular electron transfer (EET). This review focuses on the key advances of recent anode modification materials, as well as the current understanding of the microbial EET process occurring at the bacteria‐electrode interface. Based on the difference in combination mode of the exoelectrogens and nanomaterials, anode surface modification, hybrid biofilm construction and single‐bacterial surface modification strategies are elucidated exhaustively. The inherent mechanisms may help to break through the performance output bottleneck of MFCs by rational design of EET‐related nanomaterials, and lead to the widespread application of microbial electrochemical systems.