<p>The objective of this work is to create innovative nanocomposite films by integrating nanostructures (bismuth oxide Bi₂O₃ and silicon dioxide SiO₂) into polystyrene (PS). The primary objective of this study was to examine the structural and optical characteristics of nanostructures made up of PS-Bi₂O₃-SiO₂. The FTIR spectra indicate the existence of a physical contact between the original polymer and nanoparticles. At a concentration of 6 wt.%, optical microscope findings indicate the formation of a cohesive network of (Bi₂O₃-SiO₂) nanoparticles inside the polymer matrix, which is different from the pure (PS) film. The optical properties of pure PS, such as extinction coefficient (K), absorption index (α), absorbance (A), refractive index (n), and optical conductivity(σ_op), showed a positive correlation with the higher concentration of (Bi₂O₃-SiO₂) nanoparticles. Thus, these findings indicate that the material may be appropriate for various optoelectronic devices, including solar cells, transistors, electronic gates, photovoltaic cells, lasers, diodes, and other related applications. The integration of nanoparticles leads to an increase in the third-order nonlinear susceptibility (χ⁽³⁾), linear susceptibility (χ⁽¹⁾), Urbach energy (E_u), average oscillator wavelength (λ_o), nonlinear refractive index (n₂), and static refractive index (n_o). Conversely, there is a noticeable reduction in the average oscillator strength (S_o), dispersion energy (E_d), and single-oscillator energy (E_osc). The analysis of the dielectric properties of (PS-Bi₂O₃-SiO₂) nanocomposites revealed that an increase in the concentration of (Bi₂O₃-SiO₂) nanoparticles resulted in a corresponding rise in the ε', ε", and σ_a.c of pure PS. The PS-Bi₂O₃-SiO₂ nanocomposites show considerable gamma ray attenuation coefficients, according to the study. This paper suggests that these nanocomposites can be used in optoelectronic nanodevices and gamma radiation shielding.</p>