To address the limitations of contemporary lithium-ion batteries, particularly their low energy density and safety concerns, all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming alternative. Among the various SEs, organic–inorganic composite solid electrolytes (OICSEs) that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale applications. However, OICSEs still face many challenges in practical applications, such as low ionic conductivity and poor interfacial stability, which severely limit their applications. This review provides a comprehensive overview of recent research advancements in OICSEs. Specifically, the influence of inorganic fillers on the main functional parameters of OICSEs, including ionic conductivity, Li+ transfer number, mechanical strength, electrochemical stability, electronic conductivity, and thermal stability are systematically discussed. The lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic perspective. Besides, the classic inorganic filler types, including both inert and active fillers, are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of OICSEs. Finally, the advanced characterization techniques relevant to OICSEs are summarized, and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.
