This present work discusses dual-blend green polymer electrolyte (GPE)-based natural polymers, composed of carboxyl methylcellulose (CMC) and chitosan (CS), created by introducing various compositions of ammonium bromide (NH 4 Br) as a dopant in the system. These GPEs were successfully prepared by the solution casting technique and characterized using electrical impedance spectroscopy (EIS). From EIS measurement, the highest room-temperature conductivity is 1.21 × 10 -5 Scm -1 for the sample containing 20 wt.% of NH 4 Br. Plot of the temperature dependence of the GPEs revealed that the system obeys the Arrhenius rule and was thermally assisted. Besides that, dielectric studies were also conducted and the data were analyzed using complex permittivity, e*, and complex electrical modulus, M*, to determine the sample with the highest conductivity value. Thus, this study confirmed non-Debye behavior in the sample.