Non-flammable polymer gel electrolytes (NPGE) consisting of 1.0moldm−3 (=M) LiBF4/EC+DEC+TEP (55:25:20 volume ratio)+PVdF-HFP (EC: ethylene carbonate, DEC: diethyl carbonate, TEP: triethylphosphate, PVdF-HFP: poly(vinyledenefluoride-co-hexafluoropropylene)) have been developed for rechargeable lithium batteries. The effects of addition of Lewis-acid polymer (LAP) with different mole ratio in NPGE have been studied. The addition of LAP improved physico-chemical properties of NPGE, viz ionic conductivity and lithium ion transport number, as well as mechanical and thermal properties. The ionic conductivity of the gel electrolyte containing LAP reached that of the base solution electrolyte (1.0M LiBF4/EC+DEC+TEP (55:25:20)) along with better mechanical properties. Interfacial resistance at Li-metal electrode/NPGE was also improved by introducing LAP in the gel.