1,3-dioxolane　(DOL)　shows　low　interfacial　impedance　and　high　Coulombic　efficiency,　thus　its　polymer　electrolytes　have　attracted　extensive　attention.　In　order　to　initiate　DOL　polymerization,　catalyst　amount　of　LiPF6　is　usually　used　rather　than　as　the　main　lithium　salt.　Totally　replacement　of　LiTFSI　with　low　cost　of　LiPF6　could　bring　the　heat　explosion　and　high　viscosity　when　mixing　DOL　with　0.9　M　LiPF6　electrolyte　(carbonate　ester　solvent).　Here,　based　on　the　Lewis　acid-base　interaction,　a　new　type　of　Lewis　base,　pyridine,　is　added　to　control　the　explosive　polymerization　of　1,3-dioxolane　in　LiPF6　electrolyte.　Through　tuning　the　pyridine　content,　the　gelling　process　and　electrochemical　properties　could　be　controlled.　It　is　demonstrated　that　the　optimized　monomer　conversion　and　electrochemical　window　are　up　to　85.2　%　and　4.6　V;　meanwhile,　the　optimized　conductivity　and　transfer　number　are　0.99　×　10−3　S/cm　(25　°C)　and　0.68,　respectively.　The　stable　interface　between　PDOL　and　lithium　metal　anode　could　be　proved　by　the　stable　over-potential　(50mv,　700　h)　at　current　density　of　0.5　mA　cm−2.　After　500　cycles　at　2C,　the　assembled　Li/PDOL@py0.125/LiFePO4　battery　delivers　115　mAh/g　and　90　%　capacity　retention,　with　high　average　Coulombic　efficiency　of　99.83　%.　The　present　results　demonstrate　the　heat　suppression　role　of　pyridine　toward　mixing　DOL　with　0.9　M　LiPF6　electrolyte,　which　solves　the　heat　and　viscosity　problems　for　PDOL　based　gelling　polymer　electrolytes.　©　2024　Elsevier　Ltd