Synthesis and ion transport characterization of hot-pressed poly(ethylene oxide) PEO-based solid polymer electrolytes (SPEs): (1 – x) PEO: x NaClO4, where 0 < x < 50 wt.%, are reported. The composition: (70PEO: 30NaClO4) with ionic conductivity (σ) ~ 7.07 × 10−7 S cm−1 shows the highest conducting composition and this have been referred to as optimum conducting composition (OCC). Materials characterization and thermal behavior of the present SPEs have been done with the help of XRD, FTIR, SEM, DSC and TG analysis. To determine the activation energy, temperature dependent ionic conductivity (σ) of different compositions has been measured. Ionic nature of the SPEs has been explained with the help of ionic transference number (tion) measurements. Finally, the thin film polymer battery is also fabricated using the SPE OCC as electrolyte and calculated their cell parameters at room temperature.