AbstractElectrical energy and chemical energy play an important role in developing the emerging intelligent vehicle and artificial intelligence. Essentially, in well‐designed energy devices, they can be converted with each other and stored based on electrochemical reactions. Since the eventual performance relates closely with the physiochemical properties of the electrode catalysts, it is crucial to tune their microstructure to enhance the reaction kinetics and performance of energy devices. Benefitted from its superb spatial distribution of exsolved nanoparticles and uniquely anchored architecture, exsolution is a robust technique to improve performance for energy conversion and storage. Here, we review the characteristics and mechanisms of exsolution to provide solid knowledge on rationally designing and fabricating of novel exsolution‐derived energy products with excellent properties. Moreover, to trigger inspirations to create new types of energy devices and widen the application window, the recent advances in the exsolution application in energy areas covering fuel cells, electrolysers and batteries, and the fundamental principles of the exsolution effect on tuning their performance are comprehensively reviewed and analyzed. Lastly, the potential directions to further improve the energy devices' performance are discussed.