Abstract Polymer electrolytes‐based lithium metal batteries have attracted much more attention for next‐generation energy storage devices owing to their high energy density and superior safety characteristics. However, there are still some obstacles to ameliorate interfacial compatibility between conventional polymer electrolytes with lithium metal anode and high‐voltage cathodes. It is noted that poly (maleic anhydride) copolymers (PMAC)‐based polymer electrolytes (PEs) exhibit superior interfacial compatibility with both lithium metal anode and high‐voltage cathodes in virtue of their distinctive structure. These superb characteristics will endow PMAC‐based PEs very promising candidate to develop highly safe and high‐energy‐density lithium metal batteries. So far, PMAC‐based PEs have been widely used in lithium metal batteries and high‐voltage lithium metal batteries because of their prominent advantages. Herein, recent key advances of PMAC‐based PEs are summarized. The key factors affecting ionic conductivity are elaborated in terms of structural control of PMAC, lithium salts, fillers, and plasticizers. Moreover, the interfacial compatibility of PMAC‐based PEs with lithium metal anode and high‐voltage cathodes is also discussed in details. Furthermore, potential challenges and prospects of PMAC‐based PEs are also envisioned at the end of this review. It is believed that this review will shed light on highly safe and high‐energy‐density lithium metal batteries.
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