Polyethylene oxide–NaClO3 composite have been prepared by solution casting technique with different weight percentages as a polymer electrolyte for battery application. The prepared composites were characterized by various tools like XRD, FTIR and SEM. The X-ray diffraction analysis shows the complexation of polymer with salt and existence of both crystalline and amorphous phases. From FTIR spectra confirms the formation of PEO–NaClO3 composites. SEM images shows the grains are highly agglomerated and its average size increases with increase in salt ratio. Frequency dependence of dielectric property and ac electrical conductivity of polymer electrolytes were studied within the frequency range of 50Hz to 5MHz using complex impedance analysis technique. Ionic conductivity follows Arrhenius type behavior as a function of temperature. The fabricated cell of 25wt.% of PEO–NaClO3 composites generated high current of 1.79A.