This study investigates the physical and optical properties as well as the radiation shielding capacity of polyvinyl chloride (PVC) loaded with x% of bismuth vanadate (BiVO4) (x = 0, 1, 3, and 6 wt%). As a non-toxic nanofiller, the designed materials are low-cost, flexible, and lightweight plastic to replace traditional lead, which is toxic and dense. XRD patterns and FTIR spectra demonstrated a successful fabrication and complexation of nanocomposite films. In addition, the particle size, morphology, and elemental composition of the BiVO4nanofiller were demonstrated through the utilization of TEM, SEM, and EDX spectra. The MCNP5 simulation code assessed the gamma-ray shielding effectiveness of four PVC + x% BiVO4nanocomposites. The obtained mass attenuation coefficient data of the developed nanocomposites were comparable to the theoretical calculation performed with Phy-X/PSD software. Moreover, the initial stage in the computation of various shielding parameters, such as half-value layer, tenth value layer, and mean free path, besides the simulation of linear attenuation coefficient. The transmission factor declines while radiation protection efficiency increases with an increase in the proportion of BiVO4nanofiller. Further, the current investigation seeks to evaluate the thickness equivalent (Xeq), effective atomic number (Zeff), and effective electron density (Neff) values as a function of the concentration of BiVO4in a PVC matrix. The results obtained from the parameters indicate that incorporating BiVO4into PVC can be an effective strategy for developing sustainable and lead-free polymer nanocomposites, with potential uses in radiation shielding applications.