All‐solid‐state lithium batteries (ASSBs) enabled by solid‐state electrolytes (SEs) including oxide‐based and sulfide‐based electrolytes have gained worldwide attention because of their intrinsic safety and higher energy density over conventional lithium‐ion batteries (LIBs). However, despite the high ionic conductivity of advanced SEs, ASSBs still exhibit high overall internal resistance, the most significant contributor of which can be ascribed to the cathode‐SE interfaces. This review seeks to clarify the critical issues regarding the cathode‐SE interfaces, including fundamental principles and corresponding solutions. First, major issues concerning electro‐chemo‐mechanical instability between cathodes and SEs and their formation mechanisms are discussed. Then, specific problems in oxides and sulfides and various solutions and strategies toward interfacial modifications are highlighted. Efforts toward the characterization and analysis of cathode‐SE interfaces with advanced techniques are also summarized. Finally, perspectives are offered on several problems demanding urgent solutions and the future development of SE applications and ASSBs.
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