Effect of ZnAl2O4 nanofillers concentration on the physical and electrochemical properties of electrospun P(VdF-co-HFP) based nanocomposite electrolyte membranes were studied. By optimizing the spinning process parameters, the bead free and an average range (0.5-1.0 mm) of diametered fibrous membranes were developed using an electrospinning technique. The nanocomposite fibrous membrane with 5 wt% ZnAl2O4 fillers showed reduction of crystallinity, good thermal stability and smooth morphology were studied by X-ray diffraction, differential scanning calorimetry and scanning electron microscopy techniques. The fibrous P(VdF-co-HFP) copolymer and nanocomposite P(VdF-co-HFP)/ZnAl2O4 polymer electrolytes were prepared by soaking the pre-pared electrospun fibrous membranes in 1 M LiPF6 in EC: DEC (1 : 1, v/v) and evaluated the wet-ability properties by electrolyte uptake method. The activated nanocomposite fibrous polymer electrolyte membrane with 5 wt% ZnAl2O4 fillers content shows high ionic conductivity of 1.59 x 10(-3) Scm(-1) at room temperature and good electrochemical stability window higher than 4.3 V. Electrochemical performance of Li/PE, NCPE/LiCoO2 CR 2032 coin cells containing the prepared fibrous polymer electrolyte (PE) and nanocomposite polymer electrolyte (NCPE) membranes with 5 wt% ZnAl2O4 filler content is evaluated at current density 0.1 C-rate over the potential range 2.8-4.2 V.