The　in-situ　polymerization　of　1,3-dioxolane　(PDOL)　in　battery　cells　has　attracted　extensive　attention,　however,　the　differences　of　Lewis　acid　initiators　on　the　DOL　monomer　conversion　(C%)　and　electrochemical　properties　has　been　ignored.　Here,　it　is　demonstrated　that　compare　with　Sn(OTf)2　Lewis　acid　initiator,　the　gelation　of　DOL　is　achieved　at　the　lower　addition　of　In(OTf)3.　By　optimizing　their　content　in　the　gelation　process,　their　C%　are　comparable　which　are　95.7　%　and　93.5　%　for　In(OTf)3　and　Sn(OTf)2,　respectively.　However,　the　higher　ionic　conductivity　(7.1　×　10−4　S　cm−1　at　room　temperature),　electrochemical　window　(~4.5　V)　and　Li+　transference　number　(0.42)　are　obtained　for　DOL　initiated　with　In(OTf)3,　due　to　its　lower　molecular　weight　which　is　helpful　to　the　intermolecular　Li+　transport　along　PDOL　main　chain;　In　addition,　the　Li/Li　symmetrical　cell　of　In(OTf)3　can　be　stably　cycled　for　＞500　h　at　3　mA　cm−2,　with　an　over-potential　of　178mv.　The　storage　and　cycling　impedances　of　half　cells　further　proves　the　stable　interface　of　In(OTf)3　initiated　DOL　toward　to　lithium　metal　in　comparison　with　those　of　Sn(OTf)2.　Scanning　electron　microscopy　results　show　a　denser　and　thinner　interface　in　the　DOL　catalyzed　by　In(OTf)3.　Finally,　the　assembled　Li/LiFePO4　battery　delivers　specific　discharge　capacity　and　capacity　retention　rates　of　115.5mAh　g−1　and　85　%,　respectively　after　300　cycles　at　1C.　Through　the　initiator　selection,　the　DOL　synthesis　and　electrochemical　properties　can　be　tuned,　which　further　broadens　the　design　idea　of　PDOL　based　solid　polymer　electrolyte.　©　2024