Poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP))-based gel polymer electrolyte (GPE) membranes are prepared by phase inversion method using urea as pore-forming agent and dimethylformamide as solvent, respectively, and the desired polymer electrolytes are obtained after being immersed the as-prepared polymer electrolyte membranes into liquid electrolytes for 1 h. Physicochemical properties of the GPEs are investigated by SEM, XRD, FT-IR, TG-DSC, EIS and LSV. When the weight ratio of urea to P(VDF-HFP) is up to 0.6:4, the results show that the polymer electrolyte membrane presents the most uniform surface with abundant interconnected micro-pores and excellent thermal stability, in which the ionic conductivity at room temperature can reach 2.671 mS cm−1 and the reciprocal temperature dependence of ionic conductivity follows Arrhenius relationship. The interfacial resistance of the Li/GPE/Li simulated cell with 0.6 g urea can rapidly increase to a steady value about 650 Ω cm−1 from the initial value about 475 Ω cm−1 during 15 days storage at 30 °C. The polymer electrolyte with 0.6 g urea can be stable at 5.3 V (vs Li/Li+) at room temperature and the assembled Li/GPE/LiCoO2 coin cell can also show good rate and cycle performance.