Poly(vinylidene fluoride-co-hexafluoropropylene) {P(VdF-HFP)} membranes incorporating 0, 6 and 10wt.% of nano-meter sized particles of SiO2 were prepared by electrospinning. These membranes served as host matrix for the preparation of polymer electrolytes (PEs) by activating with the non-volatile and safe room temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonylimide) (BMITFSI). The membranes consisted of layers of fibers with average fiber diameter of 2–5μm and had a porosity of ∼87%. PEs with SiO2 exhibited higher ionic conductivity with a maximum of 4.3×10−3 Scm−1 at 25°C obtained with 6% SiO2. The optimum PE based on the membrane with 6% SiO2 exhibited better compatibility with lithium metal electrode on storage and resulted in enhanced charge–discharge performance in Li/LiFePO4 cells at room temperature, delivering the theoretical specific capacity of 170mAhg−1 at 0.1C-rate. The PEs exhibited a very stable cycle property as well, demonstrating their suitability for lithium battery applications.