This review discusses the potential and challenges of poly(1,3-dioxolane) (PDOL)-based solid electrolytes for practical applications in polymer solid-state lithium batteries (SSLB). PDOL electrolytes offer advantages such as high ionic conductivity, good electrochemical performance, and a simple assembly process. The review highlights the polymerization mechanisms of DOL, the performance of PDOL composite electrolytes, and their applications. It also addresses the challenges associated with PDOL electrolytes, including issues like low ionic conductivity, poor interface contact, and the need for further research to enhance their performance. The review provides insights into the polymerization mechanisms of DOL, including electrochemical, electrophilic, and nucleophilic polymerization. It also discusses the role of various initiators, such as lithium salts, aluminum salts, and organic materials, in the polymerization process. The review emphasizes the importance of optimizing the polymerization process to achieve high ionic conductivity and stability. Additionally, it explores the use of plasticizers and support skeletons to enhance the performance of PDOL electrolytes. The review concludes that PDOL-based electrolytes show great potential for practical applications in SSLB, but further research is needed to overcome the challenges and optimize their performance.This review discusses the potential and challenges of poly(1,3-dioxolane) (PDOL)-based solid electrolytes for practical applications in polymer solid-state lithium batteries (SSLB). PDOL electrolytes offer advantages such as high ionic conductivity, good electrochemical performance, and a simple assembly process. The review highlights the polymerization mechanisms of DOL, the performance of PDOL composite electrolytes, and their applications. It also addresses the challenges associated with PDOL electrolytes, including issues like low ionic conductivity, poor interface contact, and the need for further research to enhance their performance. The review provides insights into the polymerization mechanisms of DOL, including electrochemical, electrophilic, and nucleophilic polymerization. It also discusses the role of various initiators, such as lithium salts, aluminum salts, and organic materials, in the polymerization process. The review emphasizes the importance of optimizing the polymerization process to achieve high ionic conductivity and stability. Additionally, it explores the use of plasticizers and support skeletons to enhance the performance of PDOL electrolytes. The review concludes that PDOL-based electrolytes show great potential for practical applications in SSLB, but further research is needed to overcome the challenges and optimize their performance.