Synthesis and ion conduction studies on SiO2 dispersed hot-pressed sodium ion conducting nano-composite polymer electrolytes (100 − x)[70PEO:30NaHCO3] + xSiO2, where x is in wt.%, are reported. The nano-composite polymer electrolytes (NCPEs) are cast by the dispersion of nano-filler SiO2 using a hot-press method in place of the traditional solution-cast technique. The effect of nano-filler SiO2 is characterized with the help of some basic ion transport parameters viz. ionic conductivity, ionic mobility, mobile ion concentration and activation energy measurements. The material characterization and polymer–salt/SiO2 complexation are reported with the help of XRD, FTIR, SEM, DSC and TGA studies. Based on SPE host and NCPE OCC, a solid state polymeric battery fabrication and cell-potential discharge characteristics are also reported at different load conditions.