Experimental investigations on a sodium ion conducting gel polymer electrolyte nanocomposite based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP), dispersed with silica nanoparticles are reported. The gel nanocomposites have been obtained in the form of dimensionally stable, transparent and free-standing thick films. Physical characterization by X-ray diffraction (XRD), Fourier transform Infra-red (FIR) spectroscopy and Scanning electron microscopy (SEM) have been performed to study the structural changes and the ion-filler-polymer interactions due to the dispersion of SiO(2) nanoparticles in gel electrolytes. The highest ionic conductivity of the electrolyte has been observed to be 4.1 x 10(-3)S cm(-1) at room temperature with -3 wt.% of SiO(2) particles. The temperature dependence of the ionic conductivity has been found to be consistent with Vogel-Tammen-Fulcher (VTF) relationship in the temperature range from 40 to 70 degrees C. The sodium ion conduction in the gel electrolyte film is confirmed from the cyclic voltammetry, impedance analysis and transport number measurements. The value of sodium ion transport number (t(Na)+) of the gel electrolyte is significantly enhanced to a maximum value of 0.52 on the 15 wt.% SiO(2) dispersion. The physical and electrochemical analyses indicate the suitability of the gel electrolyte films in the sodium batteries. A prototype sodium-sulfur battery, fabricated using optimized gel electrolyte, offers the first discharge capacity of -165 mAh g(-1) of sulfur. (C) 2011 Elsevier B.V. All rights reserved.