The membranes for gel polymer electrolyte (GPE) for lithium-ion batteries were prepared by electrospinning a blend of poly(vinylidene fluoride) (PVdF) with cellulose acetate (CA). The performances of the prepared membranes and the resulted GPEs were investigated, including scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), porosity, hydrophilicity, electrolyte uptake, mechanical property, thermal stability, AC impedance measurements, linear sweep voltammetry, and charge-discharge cycle tests. The effect of the ratio of CA to PVdF on the performance of the prepared membranes was considered. It is found that the GPE based on the blended polymer with CA:PVdF =2:8 (in weight) has an outstanding combination property-strength (11.1 MPa), electrolyte uptake (768.2 %), thermal stability (no shrinkage under 80 A degrees C without tension), and ionic conductivity (2.61 x 10(-3) S cm(-1)). The Li/GPE/LiCoO2 battery using this GPE exhibits superior cyclic stability and storage performance at room temperature. Its specific capacity reaches up to 204.15 mAh g(-1), with embedded lithium capacity utilization rate of 74.94 %, which is higher than the other lithium-ion batteries with the same cathode material LiCoO2 (about 50 %).