Porous polyethylene (PE) or nonwoven poly(vinylidene fluoride) (PVdF) separator-supported gel polymer electrolytes are realized by thermal polymerization of a precursor solution consisting of poly(ethylene glycol)diacrylate (PEGDA) and an electrolyte solution (1M LiPF6 in an equal-volume mixture of ethylene carbonate and dimethyl carbonate). The polymerization conditions are optimized to include a PEGDA content of 3wt.% in the precursor solution and subsequent heat treatment at 80°C for 10min. Even though the gelled PEGDA electrolyte has a lower ionic conductivity than the electrolyte solution, a Li x CoO2/graphite full-cell that has a gel electrolyte with optimized PEGDA content on the PVdF separator achieves a battery performance superior to the one with PE. The best battery performances achieved are a high discharge capacity (116 mAh g−1), a good high-rate capability (95 mAh g−1 at 5.0 C-rate), and a high capacity retention ratio (90%) after the 100th cycle. This enhancement is due to the incorporation of a polar electrolyte solution that is entrapped by the polar PEGDA matrix within the nonwoven PVdF separator, which is a more suitable host that is able to well absorb and preserve the gel electrolyte.