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PVA-based polymer electrolytes were prepared with various concentrations of CdCl2 using solvent casting method. Prepared polymer films were investigated using line profile analysis employing X-ray diffraction (XRD) data. XRD results show that the crystallite size decreases and then increases with increase in CdCl2. AC conductivity in these polymer increases films first and then decreases. These observations are in agreement with XRD results. The highest ionic conductivity of 1.68E − 08 Scm−1 was observed in 4% of CdCl2 in PVA polymer blend. Crystallite ellipsoids for different concentrations of CdCl2 are computed here using whole pattern powder fitting (WPPF) indicating that crystallite area decreases with increase in the ionic conductivity.