Abstract Excellent conducting solid polymer electrolyte films were prepared by using Polyvinyl alcohol (PVA) and Iron alum through a reactive blending process. The effect of the concentration of the iron alum on the conducting behavior was studied in detail by varying the concentration of the alum in the PVA matrix. The functionality was studied using the Infrared (FT-IR) spectroscopic technique. A thermal analysis of the synthesized polymer blend was made using the differential scanning calorimetric (DSC) method, indicating that the material possesses an excellent thermal response. The FT-IR and X-ray photoelectron spectroscopy (XPS) analyses confirm that the hydroxyl group of PVA is involved in the chemical reaction with the added iron alum. An X-ray diffraction (XRD) analysis confirms that the crystallinity is enhanced upon increasing the alum content. Scanning electron microscopy (SEM) along with XPS analysis reveals the presence of the desired atoms in the polymer film. The highest AC conductivity of 1.09 × 10−1 Scm−1 at 100 °C is obtained with in this system and the AC conductivity obeys the Jonscher power law.