Polymer blending and ion transport characterization of a new poly ethylene oxide (PEO) with polyvinylpyrrolidone (PVP)-based solid polymer electrolytes (SPEs): (1 - x) [70PEO:30KBrO(3)] + x PVP, where 0 < x < 20 wt%, are reported. The polymeric blending was done using a hot-press method. To explain the materials characterization, XRD, SEM, DSC and TGA studies are reported. The conductivity enhancement in SPE was explained by the direct determination of ionic mobility (mu), mobile ion concentration (n) and activation energy using different experimental techniques. Solid-state polymeric batteries were fabricated using optimum conducting composition of SPE as an electrolyte and the cell potential discharge characteristics was studied under different load conditions.