In　recent　years,　the　pursuit　of　high　electrochemical　stability　and　safety　are　considered　as　the　newly　growing　and　leading　trend　of　next-generation　lithium-ion　batteries　(LIB).　The　gelation　of　polymer　electrolytes(GPEs)　is　the　most　direct　and　effective　way　to　improve　electrochemical　performance.　Herein,　a　novel　composited　polyethylene　glycol　(PEG)　electrolyte　is　reported　with　a　dual　acceleration　conduction　effect　of　Li+　by　the　nano-TiO2　and　triethyl　phosphate　(TEP).　The　negative　ZETA　potential　of　nano-TiO2/PEG　internal　interface　promoted　the　dissociation　of　lithium　salt　by　the　unstable　adsorption　in　diffusion　layer,　which　enhanced　the　lithium　ion　migration　and　promoted　the　uniformity　of　lithium　deposition.　The　flame　retardant　TEP　improved　safety　performance,　adjusted　the　affinity　between　EO　and　Li+,　which　bestowed　it　a　high　discharge　125.7mAh/g　at　0.2C,　with　a　low　average　capacity　decay　rate　of　0.08%　per　cycle.　The　well-designed　PEG-TEP-TiO2　GPEs　showed　wide　electrochemical　window,　stable　Li+　stripping/plating,　smaller　voltage　polarizations　and　excellent　cycling　performance.　The　new　understanding　of　composite　electrolytes　provides　a　powerful　avenue　for　facilitating　the　gelation-solid-state　lithium　ion　batteries.　©　2021　Elsevier　B.V.