Plain and embedded polyvinyl pyrrolidone (PVP)/ polyvinyl alcohol PVOH (1:1) with different weights of NiO nanoparticles (x = 0.037, 0.37and 3.7 wt%) films were formed by casting technique. The prepared nanocomposites were characterized by operating X-ray diffractometer, atomic force microscope (AFM) technique, UV-Vis.–NIR spectrophotometer, and optical limiting system. The structural examination reveals a considerable interaction between the PVP and PVOH as well as NiO nanoparticles. The AFM scans revealed that the surface roughness increases with the content of the dopant. Upon adding NiO nanoparticles to the PVP/PVOH blend matrix, the width of localized states (Urbach energy) increased and a redshift of the absorption edge was observed depending on the amount of doping, which allow the tailoring of the bandgap. The analysis revealed that the absorption index (k), dielectric constant, optical conductivity, dispersion parameters, and refractive index were altered by the NiO concentration. Also, tuning the nonlinear refractive index and the optical susceptibilities (x1 & x3 ) upon increasing NiO in the blend were allowed. The transmittance and the optical limiting properties of the films reflect the ability to candidates the PVP/PVOH with 3.7 wt% NiO as UV-Visible shielding. Thus, the NiO content makes the blend matrix effective use in various optical and optoelectronic applications.