In situ polymerized 1,3-dioxolane (PDOL) is widely utilized to construct solid polymer electrolytes because of its high room-temperature ionic conductivity and good compatibility with lithium metal. However, the current polymerization additives used in PDOL do not effectively contribute to the formation of a robust solid electrolyte interphase (SEI), leading to decreased cycle life. Herein, a film-forming Lewis acid, tris(hexafluoroisopropyl) borate (THB), is demonstrated not only to be a catalyst for the ring-opening polymerization of DOL, but also an additive for the formation of a stable fluorine- and boron-rich SEI to improve the interfacial stability and suppress the Li dendrite growth. Moreover, molecular dynamics simulations and experimental results demonstrate that the introduction of THB can promote the dissociation of lithium salt and release more Li+ while the boron site can effectively restrict the free movement of TFSI− anion, thus increasing Li+ transference numbers (0.76) and ensuring the long-term cycling stability of cells. By using THB-PDOL, a stable cycling of Li||Li symmetric cell for 600 h at a capacity of 0.5 mAh cm−2 can be achieved. Furthermore, employing THB-PDOL in Li||LiFePO4 full cell enables a capacity retention of 98.64% after 300 cycles at 1C and a capacity retention of 95.39% after 200 cycles at a high temperature (60°C). At the same time, this electrolyte is also suitable for the Li||NCM523 full cell, which also achieves excellent stability of more than 180 cycles. This film-forming Lewis acid additive provides ideas for designing low-cost, high-performance PDOL-based lithium metal batteries.