The preparation of a dextran (Dex)-hydroxyethyl cellulose (HEC) blend impregnated with ammonium bromide (NH4Br) is done via the solution cast method. The phases due to crystalline and amorphous regions were separated and used to estimate the degree of crystallinity. The most amorphous blend was discovered to be a blend of 40 wt% Dex and 60 wt% HEC. This polymer blend serves as the channel for ions to be conducted and electrodes separator. The conductivity has been optimized at (1.47 ± 0.12) × 10-4 S cm-1 with 20 wt% NH4Br. The EIS plots were fitted with EEC circuits. The DC conductivity against 1000/T follows the Arrhenius model. The highest conducting electrolyte possesses an ionic number density and mobility of 1.58 × 1021 cm-3 and 6.27 × 10-7 V-1s-1 cm2, respectively. The TNM and LSV investigations were carried out on the highest conducting system. A non-Faradic behavior was predicted from the CV pattern. The fabricated electrical double layer capacitor (EDLC) achieved 8000 cycles, with a specific capacitance, internal resistance, energy density, and power density of 31.7 F g-1, 80 Ω, 3.18 Wh kg-1, and 922.22 W kg-1, respectively.