A new highly ion conductive plasticized organic–inorganic hybrid electrolyte membrane based on triblock co-polymer poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) (ED2003), poly(ethylene glycol) diglycidyl ether (PEGDGE), poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF–HFP), 2,4,6-trichloro-1,3,5-triazine (cyanuric chloride, CC) and 3-(glycidyloxypropyl)trimethoxysilane (GLYMO) has been synthesized by a sol–gel process and characterized by a variety of experimental techniques. FTIR and 13C NMR measurements have been performed to study the molecular structure of the hybrid as well as the interactions among the constituents of the membrane. The hybrid membrane is plasticized with different electrolyte solvents and exhibits remarkable swelling ratios in the range of 670–800%. The ionic conductivity of the hybrid electrolyte membranes is varied with different electrolyte solvents and shows a maximum value of 6.9 × 10−3 S cm−1 for 1 M LiClO4 in EC/PC at 30 °C. The test cell carries initial discharge capacity of 115 mAh g−1 at a current rate of 0.2 C and shows good cycling performance up to 100 cycles and coulombic efficiency of 98–99% for the entire cycles. The plasticized organic–inorganic hybrid electrolyte membrane holds promise for applications in lithium polymer batteries.