This review focuses on the poly(1,3-dioxolane) (PDOL) electrolyte, a promising candidate for solid polymer electrolytes in polymer solid-state lithium batteries (SSLB). PDOL-based electrolytes exhibit high ionic conductivity, good electrochemical performance, and a simple assembly process. The review covers the polymerization mechanism of DOL, the performance of PDOL composite electrolytes, and their applications. It highlights the advantages of in-situ polymerization, which addresses issues such as poor interface contact and uniform Li+ deposition. The review also discusses the challenges associated with PDOL electrolytes, including low voltage tolerance and mechanical strength, and provides recommendations for future research directions. Key aspects include the role of initiators in PDOL polymerization, the formation of stable SEI layers, and the use of plasticizers and support skeletons to enhance performance. The paper aims to provide a comprehensive understanding of PDOL-based polymer electrolytes and their potential for practical application in high-voltage lithium batteries.This review focuses on the poly(1,3-dioxolane) (PDOL) electrolyte, a promising candidate for solid polymer electrolytes in polymer solid-state lithium batteries (SSLB). PDOL-based electrolytes exhibit high ionic conductivity, good electrochemical performance, and a simple assembly process. The review covers the polymerization mechanism of DOL, the performance of PDOL composite electrolytes, and their applications. It highlights the advantages of in-situ polymerization, which addresses issues such as poor interface contact and uniform Li+ deposition. The review also discusses the challenges associated with PDOL electrolytes, including low voltage tolerance and mechanical strength, and provides recommendations for future research directions. Key aspects include the role of initiators in PDOL polymerization, the formation of stable SEI layers, and the use of plasticizers and support skeletons to enhance performance. The paper aims to provide a comprehensive understanding of PDOL-based polymer electrolytes and their potential for practical application in high-voltage lithium batteries.