Lithium-ion batteries (LIBs) have been widely applied in electronic communication, transportation, aerospace, and other fields, among which separators are vital for their electrochemical stability and safety. Electrospun polyvinylidene fluoride (PVDF)-based separators have a large specific surface area, high porosity, and remarkable thermal stability, which significantly enhances the electrochemistry and safety of LIBs. First, this paper reviewed recent research hotspots and processes of electrospun PVDF-based LIB separators; then, their pivotal parameters influencing morphology, structures, and properties of separators, especially in the process of electrospinning solution preparation, electrospinning process, and post-treatment methods were summarized. Finally, the challenges of PVDF-based LIB separators were proposed and discussed, which paved the way for the application of electrospun PVDF-based separators in LIBs and the development of LIBs with high electrochemistry and security.