The solution cast process is used to set up chitosan: dextran-based plasticized solid polymer electrolyte with high specific capacitance (228.62 F/g) at the 1st cycle. Fourier-transform infrared spectroscopy (FTIR) pattern revealed the interaction between polymers and electrolyte components. At ambient temperature, the highest conductive plasticized system (CDLG-3) achieves a maximum conductivity of 4.16 × 10-4 S cm-1. Using both FTIR and electrical impedance spectroscopy (EIS) methods, the mobility, number density, and diffusion coefficient of ions are measured, and they are found to rise as the amount of glycerol increases. Ions are the primary charge carriers, according to transference number measurement (TNM). According to linear sweep voltammetry (LSV), the CDLG-3 system's electrochemical stability window is 2.2 V. In the preparation of electrical double layer capacitor devices, the CDLG-3 system was used. There are no Faradaic peaks on the cyclic voltammetry (CV) curve, which is virtually rectangular. Beyond the 20th cycle, the power density, energy density, and specific capacitance values from the galvanostatic charge-discharge are practically constant at 480 W/Kg, 8 Wh/Kg, and 60 F g-1, for 180 cycles.