In the present work, the casting process was used to prepare polymeric films based on Polyvinyl alcohol/Polyvinylpyrrolidone (PVA/PVP)loaded with various weight percentages of HgCl2. The morphology and the microstructure of the synthesized samples were studied using Scanning Electron Microscope (SEM), Atomic force microscope (AFM), x-Ray Diffraction (XRD), and Fouriertransform infrared spectroscopy (FT-IR)techniques. UV/VIS/NIR spectrophotometer was implemented to scientifically check the optical elucidation. All films between the two phases are characterized by substantial integration of HgCl2 and PVA/PVP. The scanning electron microscope shows a morphology modification of the blend surface with the mercuric chloride substantive. The roughness calculated from AFM images increased with increasing HgCl2. The agglomeration of the particles made a significant influence on the optical transmittance properties of pure PVA/PVP. Due to the growth of distortion and imperfection in the structure of the blend matrix by the addition of HgCl2, there is a modification in the engineering bandgap, localized state’s order, coefficient of absorption, and optical conductivity. The dispersion and oscillator energies were calculated using the Wemple and Di Domenico (DDW) model for a single oscillator. Various theoretical relations between energy gaps and refractive indices were used to calculate the average refractive index of each sample. Further, the nonlinear refractive index and optical susceptibilities of polymer composite samples were enhanced by increasing the percentage of HgCl2. The influence of loading on the optical limiting of the blend was investigated via He-Ne and green diode lasers. The results indicate the ability to use our flexible films in various optoelectronic devices.