Polymer blends of polyvinyl chloride/nitrocellulose/MoS2‐Nafion (PVC/NC/MoS2‐Nafion) were prepared using a casting technique. FTIR analysis revealed chemical interactions between the polymer matrix and filler. XRD analysis was employed to investigate changes in structural phases, while SEM illustrated the agglomerated morphology of the modified blends. The critical role of ionic interaction between Nafion and polymer system in enhancing electrical properties was confirmed through impedance analysis. The introduction of oxygenated functionalities improved surface topography and roughness, as observed by AFM. Electrical conductivity increased from 10−6 S/cm to 10−4 S/cm, accompanied by a decrease in activation energy (Ea). The addition of Nafion decreased bulk resistance, indicating enhanced ionic mobility, as supported by impedance analysis. TG‐DSC analysis demonstrated that MoS2 and Nafion improved thermal properties of polymer blends. The glass transition temperature (Tg) increased by approximately 13 °C and 21 °C with MoS2 and Nafion, respectively. Universal testing machine (UTM) results indicated moderate tensile strength and Young's modulus achieved by MoS2 and Nafion. With increasing Nafion loading, elongation at break rose to around 71 %, showcasing excellent interfacial interaction in polymer‐filler system. The resulting polymer blends, modified by Nafion, exhibited high ionic/electrical conductivity and show promise for hybrid polymer electrolyte applications.