Gel polymer electrolyte films based on thermoplastic polyurethane (TPU)/poly(vinylidene fluoride) (PVdF) with and without in situ ceramic fillers (SiO2 and TiO2) are prepared by electrospinning 9wt% polymer solution at room temperature. The electrospun TPU–PVdF blending membrane with 3% in situ TiO2 shows a highest ionic conductivity of 4.8×10−3 Scm−1 with electrochemical stability up to 5.4V versus Li+/Li at room temperature and has a high tensile strength (8.7±0.3MPa) and % elongation at break (110.3±0.2). With the superior electrochemical and mechanical performance, it is very suitable for application in polymer lithium ion batteries.