In this study, a composite polymer matrix for gel polymer electrolyte (GPE) is prepared by the electrospinning process, combining poly(vinylidene fluoride-co-hexafluoropropylene) and nano-sized Al2O3 ceramic particles. The composite matrix is impregnated with a liquid electrolyte to prepare the GPE-Al2O3 composite and its properties are compared with those of pure GPE. The GPE-Al2O3 composite improves the interfacial resistance, ion coordination and the electrochemical stability of the GPE. The electrochemical performances are analyzed by applying the GPEs to LiNi1/3Mn1/3Co1/3O2 (NMC) and Li4Ti5O12 (LTO) cells. The GPE-Al2O3 composite exhibits a higher discharge capacity than the GPE at 0.1 C-rate and excellent performance in both the LTO and the NMC half-cells under cyclic conditions. The GPE-Al2O3 composite shows good compatibility and high electrochemical property on LTO/NMC full-cell.