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This work focuses on polymer electrolytes composed of a starch-chitosan blend host, ammonium iodide (NH 4 I) and glycerol. Fourier transform infrared (FTIR) analysis confirms the interaction of starch-chitosan-NH 4 I-glycerol. The highest room temperature conductivity is (1.28 ± 0.07) × 10 −3 S cm −1 , obtained by a sample containing 30 wt% glycerol. Dielectric studies showed that the electrolytes obeyed non-Debye behavior. The total ionic transference number for the 30 wt% glycerol sample was 0.991, and the conduction mechanism for this sample followed the quantum mechanical tunneling (QMT) model. Linear sweep voltammetry (LSV) showed that this sample was electrochemically stable up to 1.90 V. The highest conducting sample was used in the fabrication of an electrical double layer capacitor (EDLC) cell.