Two polymer (poly(ethylene oxide) and poly(vinylpyrrolidone))-based sodium ion conducting systems have been studied. The conductivity and related parameters has been compared after irradiation with that before irradiation. The complex impedance spectroscopic tools have been used to determine the ionic conductivity, dielectric constant, number of charge carriers, and its corresponding mobility of the two systems. Modulation in conductivity of the systems has been correlated and attributed to change in crystallinity of the matrix. Suggestive principles have also been proposed for preparation of optimum polymer electrolyte films using ion beam treatment.