The novel polyvinyl alcohol (PVA) films reinforced with varied concentrations of Mn2O3/reduced graphene oxide (rGO) nanoparticles (NP) are prepared via the casting technique. A hydrothermal approach methodology is used to prepare manganese oxide reduce graphene oxide (Mn2O3/rGO) composite. The X-ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscope (SEM), and optical microscope setups are used to study the impact of nanoparticles on the structure of the PVA matrix. The surface roughness was measured and found to increase with increasing NPs concentration in the polymer matrix. The UV–vis spectroscopy is used to investigate the optical absorption and transmission data for the prepared films. The addition of Mn2O3/rGO NP in the polymer matrix effects on the optical parameters like the absorption coefficient, optical bandgap, refractive index, and optical conductivity. The optical bandgap of PVA films with Mn2O3/rGO NP is lower than that of PVA pure. The refractive index and optical conductivity were tuned with the addition of Mn2O3/rGO NP. The PVA-Mn2O3/rGO films are promising material for various opto-electronic fields.