Novel hybrid (organic/inorganic) electrospun nanocomposite polymer blend electrolyte fibrous membranes with the composition poly(vinylidene difluoride-co-hexafluoropropylene) [P(VdF-co-HFP)]/poly(methyl methacrylate) [P(MMA)]/magnesium aluminate (MgAl2O4)/LiPF6 were prepared by the electrospinning technique. All of the prepared electrospun P(VdF-co-HFP); PMMA blend [90% P,-(VdF-co-HFP)/10% PMMA]; and, nanocomposite polymer blend [90% P(VdF-co-HFP)/10% PMMA/x wt % MgAl2O4 (x = 2, 4, 6, and 8)] fibrous membranes were characteriZed by X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, and scanning electron microscopy. The fibrous nanocomposite separator-cum-polymer blend electrolyte membranes were obtained by soaking the nanocomposite polymer blend membranes in an electrolyte solution containing 1 M LiPF6 in ethylene carbonate (EC)/diethyl carbonate (DEC),(1:1, v/v). The newly - developed fibrous, nanocomposite polymer blend electrolyte [90% P(VdF-co-HFP)/10% PMMA/6 wt % MgAl2O4/LiPF6] membrane showed a low crystallinity, low average fiber diameter, high thermal stability, high electrolyte uptake, high conductivity (2.60 10(-3) S cm(-1)) at room temperature, and good potential stability above 4.5 V. The best properties of the fibrous nanocomposite polymer blend electrolyte (NCPBE) membrane with a 6 wt % MgAl2O4 filler content was used for the fabrication of a Li/ NCPBE/LiCoO2 CR, 2032 coin cell. The electrochemical performance Of the fabricated CR 2032 cell was evaluated at a current density of 0.1 C-rate. The fabricated CR 2032 cell lithium battery using the newly developed NCPBE membrane delivered an initial discharge capacity of 166 mAh g(-1) and a stable cycle performance.