A novel electrospun gel polymer electrolyte (GPE) consisting of thermoplastic polyurethane (TPU) and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) is prepared and investigated. Its characteristics are investigated by scanning electron microscopy (SEM), thermal analysis (TGA). The GPE shows a maximum ionic conductivity of 4.1 × 10−3 S cm−1 with electrochemical stability up to 5.5 V versus Li+/Li at room temperature. In addition, it shows a first charge–discharge capacity of 168.8 mAh g−1 when the gel polymer electrolyte (GPE) is evaluated in a Li/PE/LiFePO4 cell under 0.1 C-rate at the first cycle. What's more, there is microscale attenuation (1%) in the 30 cycles of charge and discharge tests. The TPU/PVDF-HFP membrane has a high tensile strength (8.4 ± 0.3 MPa) and elongation at break (118.7 ± 0.2)%. With the outstanding electrochemical and mechanical performance, it is very suitable for application in polymer lithium ion batteries.