Electrospun pure and hybrid nanocomposite PMMA blend fibrous electrolyte membranes with various x wt% of ZnAl2O4, (x = 2, 4, 6 and 8) ceramic fillers were prepared by an electrospinning technique. All the prepared electrospun pure P(VdF-co-HFP), PMMA blend [90% P(VdF-co-HFP)/10% PMMA] and nanocomposite PMMA blend [90% P(VdF-co-HFP)/10% PMMA/x wt% ZnAl2O4, (x = 2, 4, 6 and 8)] fibrous membranes were characterized systematically using X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry and scanning electron microscopy. The activated separator-cum-nanocomposite PMMA blend fibrous electrolyte membranes were obtained by soaking in an organic liquid electrolyte solution containing 1 M LiPF6 in EC : DEC (1 : 1, v/v). The newly developed novel nanocomposite PMMA blend fibrous electrolyte [90% P(VdF-co-HFP)/10% PMMA/6 wt% ZnAl2O4/LiPF6] membrane showed low crystallinity, high thermal stability, low average fiber diameter, high electrolyte uptake, high conductivity (4.135 x 10(-3) S cm(-1)) at room temperature and good potential stability above 4.5 V. The optimized best composition of nanocomposite PMMA blend fibrous electrolyte membranes with 6 wt% ZnAl2O4 filler content is used for the fabrication of a (Li/NCPBE/LiCoO2) CR 2032 coin type lithium cell. The fabricated CR 2032 lithium coin cell containing the newly developed nanocomposite polymer blend electrolyte (NCPBE) membrane delivers an initial discharge capacity of 157 mA h g(-1) and also exhibits stable cycle performance at a current density of 0.1C rate at room temperature.