Gel polymer electrolyte films based on thermoplastic polyurethane (TPU) and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) (1/1, w/w) were prepared by electrospinning polymer. The highest ionic conductivity was 6.62 x 10(-3) S cm(-1) for 10 wt% electrolyte solution at room temperature. And, high value of tensile strength (9.8 +/- 0.2 MPa) and elongation at break (121.5 +/- 0.2 %) existed. The Li/PE/LiFePO4 cell with the gel polymer electrolyte (GPE) delivered a high initial discharge capacity of 163.49 mAh g(-1) under 0.1 C rate and exhibited microscale attenuation (5.5 %) after 50 cycles. With the excellent characteristics, it is suitable for practical application in polymer lithium-ion batteries.