A series of nanocomposite polymer electrolytes (NCPEs) comprising nanoparticles of BaTiO3, Al2O3 or SiO2 were prepared by electrospinning technique. The nano-sized ceramic fillers were incorporated into poly(vinylidene fluoride-co-hexafluoropropylene) [P(VdF-HEP)] membranes during the electrospinning process. The resultant porous membranes are good absorbent of the liquid electrolyte and exhibit high electrolyte retention capacity. The presence of the ceramic nanoparticles has positive effect on the mechanical properties of the membranes. The ionic conductivity and the electrochemical stability window of the electrospun P(VdF-HFP)-based polymer are enhanced by the presence of the fillers. The cell Li/LiFePO4 based on the NCPE containing BaTiO3 delivers a discharge capacity of 164mAh/g, which corresponds to 96.5% utilization of the active material. In comparison, the performance of Li/LiFePO4 cells with NCPEs containing Al2O3 and SiO2 was observed to be lower with respective discharge capacities of 153 and 156mAh/g. The enhanced performance of the BaTiO3-based-NCPE is attributed mainly to its better interaction with the host polymer and compatibility with lithium metal.