AbstractThe ever‐growing demand in modern power systems calls for the innovation in electrochemical energy storage devices so as to achieve both supercapacitor‐like high power density and battery‐like high energy density. Rational design of the micro/nanostructures of energy storage materials offers a pathway to finely tailor their electrochemical properties thereby enabling significant improvements in device performances and enormous strategies have been developed for synthesizing hierarchically structured active materials. Among all strategies, the direct conversion of precursor templates into target micro/nanostructures through physical and/or chemical processes is facile, controllable, and scalable. Yet the mechanistic understanding of the self‐templating method is lacking and the synthetic versatility for constructing complex architectures is inadequately demonstrated. This review starts with the introduction of five main self‐templating synthetic mechanisms and the corresponding constructed hierarchical micro/nanostructures. Subsequently, the structural merits provided by the well‐defined architectures for energy storage are elaborately discussed. At last, a summary of current challenges and future development of the self‐templating method for synthesizing high‐performance electrode materials is also presented.