This report presents the preparation of plasticized sodium ion-conducting polymer electrolytes based on polyvinyl alcohol (PVA)via solution cast technique. The prepared plasticized polymer electrolytes were utilized in the device fabrication of electrical double-layer capacitors (EDLCs). On an assembly EDLC system, cyclic voltammetry (CV), electrical impedance spectroscopy (EIS), linear sweep voltammetry (LSV), transfer number measurement (TNM) and charge-discharging responses were performed. The influence of plasticization on polymer electrolytes was investigated in terms of electrochemical properties applying EIS and TNM. The EIS was fitted with electrical equivalent circuit (EEC) models and ion transport parameters were estimated with the highest conductivity of 1.17 × 10-3 S cm-1 was recorded. The CV and charge-discharging responses were used to evaluate the capacitance and the equivalent series resistance (ESR), respectively. The ESR of the highest conductive sample was found to be 91.2 Ω at the first cycle, with the decomposition voltage of 2.12 V. The TNM measurement has shown the dominancy of ions with tion = 0.982 for the highest conducting sample. The absence of redox peaks was proved via CV, indicating the charge storing process that comprised ion accumulation at the interfacial region. The fabricated EDLC device is stable for up to 400 cycles. At the first cycle, a high specific capacitance of 169 F/g, an energy density of 19 Wh/kg, and a power density of 600 W/kg were obtained.