Large-scale production of green and pollution-free materials is crucial for deploying sustainable clean energy. Currently, the fabrication of traditional energy materials involves complex technological conditions and high costs, which significantly limits their broad application in the industry. Microorganisms involved in energy production have the advantages of inexpensive production and safe process and can minimize the problem of chemical reagents in environmental pollution. This paper reviews the mechanisms of electron transport, redox, metabolism, structure, and composition of electroactive microorganisms in synthesizing energy materials. It then discusses and summarizes the applications of microbial energy materials in electrocatalytic systems, sensors, and power generation devices. Lastly, the research progress and existing challenges for electroactive microorganisms in the energy and environment sectors described herein provide a theoretical basis for exploring the future application of electroactive microorganisms in energy materials.