Polyvinyl alcohol (PVA) and Polyvinyl Pyrrolidone (PVP) based polymer electrolytes for different loading wt% of CdCl2 were prepared by solution casting. The structural complexation was confirmed and interlayer spacing (d) was evaluated by using X-ray diffraction (XRD) study. The chemical bonding between polymer and salt was identified by using Fourier transform infrared spectroscopy (FTIR) technique. The FTIR peak at 3402.43 cm -1 in addition of PVP in PVA/CdCl2 composite demonstrates the grafting between two polymers. The presence of ionic bright channels and variation in morphology for different loading wt% of CdCl2 was confirmed by scanning electron microscope (SEM) and was also verified by Atomic force microscopy (AFM) micrographs. The analysis of impedance spectroscopy represented by semicircular pattern is driven by conduction mechanism and correlated with electrical conductivity. The enhanced AC conductivity of polymer electrolyte is directly proportional to frequency (50Hz-1MHz). The maximum value of DC conductivity 1.65x10 -5 S/m evaluated from Arrhenius plots and attribute to high mobility of free charges at higher temperature. The evaluated results of structural, morphological and electrical properties of present composites make the present research good for electrochemical devices.