Polyethylene oxide (PEO)-polyvinylpyrrolidone (PVP) blended Na,+, ion conducting solid polymeric membranes: (1−,x,) [75PEO:25NaPO,3,] + ,x, PVP, where 0 ,<,x,<, 12 wt%, are reported. The polymeric blending was done using a solvent-free hot-press method. Two orders of conductivity enhancement (,σca,. 1.07 × 10,−5, S⋅cm,−1,) have been achieved with 3 wt% of PVP (,i.e., the composition: [97(75PEO:25NaPO,3,) + 3PVP]), from that of the pure host: (75PEO:25NaPO3). The conductivity enhancement in PEO-PVP blended solid polymeric membranes have been explained by the ionic conductivity, ionic mobility and mobile ion concentration measurements. Materials characterization and polymer-salt complexation were done with the help of X-ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermo gravimetric analysis (TGA) studies. The temperature dependent conductivity studies have also been done to compute the activation energy (,E,a,) values from lgσ,−,1/,T, Arrhenius plots. A solid state polymeric battery was fabricated by using optimum conducting composition of solid polymer electrolyte (SPE OCC), and some important cell parameters were also calculated from the discharge profile of the cell.