Gel polymer electrolyte films based on poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP), thermoplastic polyurethane (TPU) and poly(methyl methacrylate) (PMMA) with and without in situ SiO2 fillers are prepared by electrospinning a polymer solution at room temperature. The electrospun PVDF-HFP/ TPU/PMMA blending membrane with 2% in situ SiO2 shows a highest ionic conductivity of 8.5 x 10(-3) S cm(-1) with electrochemical stability up to 5.9 V versus Li+/Li at room temperature. In addition, it shows a first charge of 168.5 mA h g(-1), which is about 99% of the theoretical capacity of LiFePO4; the tensile strength of the PVDF-HFP/TPU/PMMA membrane is 10.8 MPa with elongation-at-break at 86.4%. With the outstanding electrochemical and mechanical performance, it is very suitable for application in polymer lithium batteries.