Polymer electrolytes have aroused wide interest in lithium batteries, but their comprehensive performances (including ionic conductivity, electrochemical window, and mechanical strength) need to be enhanced for high‐energy lithium batteries. A rigid–flexible coupling strategy is proposed to enhance the comprehensive performances of polymer electrolytes. To date, “rigid–flexible coupling” has been widely applied in gel and solid polymer electrolytes. For many kinds of polymer electrolytes, their ionic conductivity, electrochemical window, interfacial stability, and mechanical properties are significantly improved by “rigid–flexible coupling,” breaking their inherent application barriers in high‐energy lithium battery. Herein, recent key progress in rigid–flexible coupling polymer electrolytes is reviewed in terms of their design concepts, chemical‐physical properties, electrochemical performances, and battery properties. This overview also conducts a perspective for rigid–flexible coupling polymer electrolytes. It is hoped that fresh and established researchers can obtain a clear perspective of “rigid–flexible coupling” and this mini review can also throw light on the exploration of high‐energy polymer lithium batteries. The “rigid–flexible coupling” strategy has significantly improved ionic conductivity, electrochemical window, and mechanical properties of many polymer electrolytes, breaking their inherent application barriers in lithium batteries. This paper reviews recent progress in rigid–flexible coupling polymer electrolytes and conducts their perspectives and challenges, hoping to obtain a clear perspective of “rigid–flexible coupling” and throw light on the exploration of high‐energy polymer lithium batteries.