Composite membranes of poly(vinylidene fluoride-co-hexafluoropropylene) {P(VdF-HFP)} and different composition of silica have been prepared by electrospinning polymer solution containing in situ generated silica. These membranes are made up of fibers of 1–2μm diameters. These fibers are stacked in layers to produce fully interconnected pores that results in high porosity. Polymer electrolytes were prepared by immobilizing 1M LiPF6 in ethylene carbonate (EC)/dimethyl carbonate (DMC) in the membranes. The composite membranes exhibit a high electrolyte uptake of 550–600%. The optimum electrochemical properties have been observed for the polymer electrolyte containing 6% in situ silica to show ionic conductivity of 8.06mScm−1 at 20°C, electrolyte retention ratio of 0.85, anodic stability up to 4.6V versus Li/Li+, and a good compatibility with lithium metal resulting in low interfacial resistance. A first cycle specific capacity of 170mAhg−1 was obtained when the polymer electrolyte was evaluated in a Li/lithium iron phosphate (LiFePO4) cell at 0.1C-rate at 25°C, corresponding to 100% utilization of the cathode material. The properties of composite membrane prepared with in situ silica were observed to be comparatively better than the one prepared by direct addition of silica.