This study reports the development of a new system of porous, chemically cross-linked, gel polymer electrolytes based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF–HFP) copolymer as a polymer matrix, polyethylene glycol (PEG) as a plasticizer, and polyethylene glycol dimethacrylate (PEGDMA) as a chemical cross-linking oligomer. The electrolytes are prepared by a combination of controlled evaporation and thermal polymerization of PEGDMA. PVdF–HFP/PEG/PEGDMA gel polymer electrolytes with a composition of 5/3/2 exhibit both high ambient ionic conductivity, viz., >1mScm−1, and a high tensile modulus of 52MPa, because of their porous and network structures. All the blends of electrolytes are electrochemically stable up to 5V versus Li/Li+ in the presence of 1M LiPF6/ethylene carbonate–diethyl carbonate (EC–DEC). With these polymer electrolytes, rechargeable lithium batteries composed of carbon anode and LiCoO2 cathode have acceptable cycleability and a good rate capability.