This paper studies the structural and electrical properties of solid polymer blend electrolytes based on polyvinyl alcohol (PVA) and methylcellulose (MC) incorporated with sodium iodide (NaI). The polymer electrolyte films were assembled through a solution casting technique. The host matrix, which is doped with different NaI salt concentrations between 10 and 50 wt%, utilizes the most amorphous blend compositions (60 wt% Polyvinyl alcohol and 40 wt% methylcellulose). The structural behaviour of the electrolyte films was examined utilizing X-ray diffraction (XRD) and Fourier transformation infrared (FTIR) techniques. The semi crystalline nature of PVA:MC with inserted NaI was derived from the X-ray diffraction studies, while the XRD analysis suggests that the highest ion conductive sample displays the minimum crystalline nature. The interaction between polymer blends and inserted salt was conceived from the FTIR investigation. Shifting of peaks and variation in the intensity of FTIR bands was detected. To investigate the structural properties and calculate the degree of crystallinity of the films, the (XRD) technique was employed, while electrical impedance spectroscopy (EIS) was utilized for studying the conductivity of the samples. In order to comprehend all of the electrical properties of the ion-conducting systems, the EIS outcome of each electrolyte was matched with Equivalent Electrical Circuits ( EEC) s. Ion transport parameters including mobility, carrier density and diffusion are well assessed for the samples and the dielectric properties were compared with the conductivity measurement. At lower frequencies, the dielectric constant was elevated and dielectric loss was detected. Loss tangent and electric modulus plots were used to study the relaxation nature of the samples. The highest ambient temperature conductivity of PVA loaded 50 wt% of NaI was determined to be 1.53 × 10 −5 S/cm. The loss tangent relaxation peak shifts towards high-frequency side which indicates the decrease of relaxation time and faster ion dynamics.