Two polymer electrolyte systems consisting of polyacrylonitrile (PAN)-methylcellulose (MC) blend have been prepared using solution cast technique. For undoped material, polymer blend based films have been prepared at various PAN-MC ratios. The hydrogen bonding interaction between the two polymers is analyzed using Fourier transform infrared spectroscopy (FTIR). PAN-MC interaction is proven from the shifting of CN and OH stretching band. The undoped films have been examined using X-ray diffraction (XRD) technique to determine the most amorphous film. The blend of 50 wt.% PAN and 50 wt.% MC has been found as the most amorphous and served as the polymer host. Thermogravimetric analysis (TGA) is used to study the thermal stability of PAN, MC and PAN-MC blend films. It is revealed that PAN-MC film is thermally stable up to similar to 330 degrees C. In PAN- MC-LiI section, the complexation between the polymer host and lithium iodide (LiI) is confirmed using FTIR analysis. From XRD studies, the degree of crystallinity of PAN-MC based electrolytes is found to decrease with the incorporation of LiI up to 50 wt.%. Impedance spectroscopy technique is performed to study the effect of LiI on the conductivity and other electrical properties of electrolytes. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.