Polymer composites, which are light in weight, cost effective, and less toxic, have potential applications in X-ray and γ-ray shielding and protection. In this work, we have explored the efficacy of poly(vinyl alcohol)-bismuth oxide composites as radiation shielding materials. Poly(vinyl alcohol) composites with different wt % (0-50) of bismuth were prepared by a simple solution casting technique. Structural and thermal characterization of these samples was carried out using Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). TGA revealed the enhanced thermal stability of these composites. AC conductivity measurements and optical spectroscopy were used to analyze their electrical behavior. The composites showed low conductivity, and the energy gap obtained also showed their tendency to be insulators. The radiation attenuation properties were investigated using X-ray (5.895 and 6.490 keV) and γ-ray (59.54 and 662 keV) transmission measurements. The shielding efficiency of the composites increased with filler wt %. The 40 wt % composites exhibited mass attenuation coefficients of 122.68 and 93.02 cm 2 /g at photon energies of 5.895 and 6.490 keV, respectively, while the 50 wt % composites showed 1.57 and 0.092 cm 2 /g at photon energies of 59.54 and 662 keV, respectively. The effective atomic number quantifies the probability of interaction of radiation with matter. The effective atomic number of the composites calculated by the direct method was in good agreement with the theoretical value obtained from Auto-Zeff software.