The current work is concerned with the study and examination of the thermal and electrical characteristics of polyvinyl alcohol (PVA)/Mn2O3–reduced graphene oxide (rGO) nanocomposite. The Mn2O3–rGO composite was synthesized using a hydrothermal approach technique, and then PVA films were strengthened with varying amounts of Mn2O3–rGO nanoparticles (NP) prepared by the casting method. Raman analysis was applied to polymer films to ensure the complexation between the PVA and Mn2O3–rGO. Thermogravimetric analysis (TGA) and electrical analysis are used to investigate the effect of Mn2O3–rGO NP on the thermal stability and electrical conductivity of the polymer films. The films' thermal stability was raised by increasing the Mn2O3–rGO content in the PVA matrix. The polymer films exhibit an increase in electrical conductivity from 2.023 × 10⁻⁸ S·cm⁻¹ for pure PVA to 1.895 × 10⁻⁵ S·cm⁻¹ for PVA-1.5% Mn2O3–rGO, which arises from the rise in free charge carrier mobility and hopping ionic hopping. Furthermore, in accordance with the Arrhenius relation, conductivity increases with temperature. The results nominated the present composite in flexible electronic applications.