Mn3O4 (MO) nanoparticles have drawn a lot of attention due to their use in batteries, ion exchange, sensors, and catalysts in various oxidation states. Here, prior to developing new hybrid freestanding films with different MO nanoparticle concen trations (0, 0.037, 0.37, and 3.7 wt%), it was essential to first manage the electrical and optical properties of the PVA/PVP blend. Several methods, including high-resolution transmission electron microscopy, Atomic force microscope, FTIR, and XRD, were accustomed to verifying the emergence of the polymeric nanocomposite (PNC) films. The correlation between both the optical and dielectric properties of the films and the bandgap was altered using the doping ratio. In terms of its optical properties, MO is observed to have a significant impact on pure PVA/PVP, including the indirect optical energy gap, the localized state’s order, the absorption coefficient, and the response of optical conductivity. Hervé–Vandamme, Moss, Singh-Kumar, and Ravindra are a few models that have studied the connection between energy gaps and refractive index. Moreover, PVA/PVP/xMn3O4 polymer nanocomposite samples with varied MO levels were examined for their linear together with nonlinear optical properties (NLOP). The exclusion of both ordinary and laser light is studied in the PVA/ PVP enriched MO (NPs) samples that were created. Moreover, there are sharp decreases in the laser transmitted power from 315.88 to 13.6 mW for the pure blend to 0.135 and 0.00039 for PNC/3.75Mn3O4 nano-composition using a laser source of 623.8 and 533 nm, respectively. Thus PNC/3.75Mn3O4 sample is recognized as a good prospect for relatively inexpensive optical limiting and laser filter innovation.