In this study, plasticized films of polyvinyl alcohol (PVA): chitosan (CS) based electrolyte impregnated with ammonium thiocyanate (NH4SCN) were successfully prepared using a solution-casting technique. The structural features of the electrolyte films were investigated through the X-ray diffraction (XRD) pattern. The enrichment of the amorphous phase with increasing glycerol concentration was confirmed by observing broad humps. The electrical impedance spectroscopy (EIS) portrays the improvement of ionic conductivity from 10-5 S/cm to 10-3 S/cm upon the addition of plasticizer. The electrolytes incorporated with 28 wt.% and 42 wt.% of glycerol were observed to be mainly ionic conductor as the ionic transference number measurement (TNM) was found to be 0.97 and 0.989, respectively. The linear sweep voltammetry (LSV) investigation indicates that the maximum conducting sample is stable up to 2 V. An electrolyte with the highest conductivity was used to make an energy storage electrical double-layer capacitor (EDLC) device. The cyclic voltammetry (CV) plot depicts no distinguishable peaks in the polarization curve, which means no redox reaction has occurred at the electrode/electrolyte interface. The fabricated EDLC displays the initial specific capacitance, equivalent series resistance, energy density, and power density of 35.5 F/g, 65 Ω, 4.9 Wh/kg, and 399 W/kg, respectively.