| Summary: | Abstract Compared with commercial lithium batteries with liquid electrolytes, all‐solid‐state lithium batteries (ASSLBs) possess the advantages of higher safety, better electrochemical stability, higher energy density, and longer cycle life; therefore, ASSLBs have been identified as promising candidates for next‐generation safe and stable high‐energy‐storage devices. The design and fabrication of solid‐state electrolytes (SSEs) are vital for the future commercialization of ASSLBs. Among various SSEs, solid polymer composite electrolytes (SPCEs) consisting of inorganic nanofillers and polymer matrix have shown great application prospects in the practice of ASSLBs. The incorporation of inorganic nanofillers into the polymer matrix has been considered as a crucial method to achieve high ionic conductivity for SPCE. In this review, the mechanisms of Li+ transport variation caused by incorporating inorganic nanofillers into the polymer matrix are discussed in detail. On the basis of the recent progress, the respective contributions of polymer chains, passive ceramic nanofillers, and active ceramic nanofillers in affecting the Li+ transport process of SPCE are reviewed systematically. The inherent relationship between the morphological characteristics of inorganic nanofillers and the ionic conductivity of the resultant SPCE is discussed. Finally, the challenges and future perspectives for developing high‐performance SPCE are put forward. This review aims to provide possible strategies for the further improvement of ionic conductivity in inorganic nanoscale filler‐reinforced SPCE and highlight their inspiration for future research directions.
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