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In this study, the solution casting method was employed to prepare plasticized polymer electrolytes of chitosan (CS):LiCO 2 CH 3 :Glycerol with electrochemical stability (1.8 V). The electrolyte studied in this current work could be established as new materials in the fabrication of EDLC with high specific capacitance and energy density. The system with high dielectric constant was also associated with high DC conductivity (5.19 × 10 -4 S/cm). The increase of the amorphous phase upon the addition of glycerol was observed from XRD results. The main charge carrier in the polymer electrolyte was ion as t el (0.044) < t ion (0.956). Cyclic voltammetry presented an almost rectangular plot with the absence of a Faradaic peak. Specific capacitance was found to be dependent on the scan rate used. The efficiency of the EDLC was observed to remain constant at 98.8% to 99.5% up to 700 cycles, portraying an excellent cyclability. High values of specific capacitance, energy density, and power density were achieved, such as 132.8 F/g, 18.4 Wh/kg, and 2591 W/kg, respectively. The low equivalent series resistance ( ESR ) indicated that the EDLC possessed good electrolyte/electrode contact. It was discovered that the power density of the EDLC was affected by ESR .