Preparation and ion transport property of new Na+ ion conducting nanocomposite polymeric electrolytes (NCPEs): (1 – x)[80PEO:20NaI] + xTiO2, where 0 ≤ x ≤ 20 wt %, are reported. The present NCPEs have been synthesized by a new hot-press technique. The highest room temperature conductivity (σ ~ 4.5 × 10–5 S cm–1) has been found at the composition: [95(80PEO:20NaI) +5TiO2] and this has been referred to as optimum conducting composition (OCC). Four orders of conductivity enhancement have been achieved by the dispersion of nano filler TiO2 from that of the pure PEO (σ ~ 4.2 × 10–9 S cm–1). The ion transport properties of newly synthesized NCPEs has been discussed on the basis of experimental measurements on some basic ionic parameters viz. conductivity (σ), ionic mobility (μ), mobile ion concentration (n) and ionic transference number (tion) measurements. Material characterizations have been done with the help of scanning electron micrograph (SEM) and differential scanning calorimetry (DSC) studies. The conductivity as a function of temperature has also been studied to compute the activation energy (Ea) by least square linear fitting of “logσ–1/T” Arrhenius plot.