This work aimed to intensively study polypropylene samples (PP) embedded with micro- and nanoparticles of Bi2O3 for their application in radiation shielding. Samples were prepared by adding 10%, 20%, 30%, 40%, and 50% of Bi2O3 microparticles (mBi2O3) by weight, and adding 10% and 50% of Bi2O3 nanoparticles (nBi2O3), in addition to the control sample (pure polypropylene). The morphology of the prepared samples was tested, and also, the shielding efficiency of gamma rays was tested for different sources with different energies. The experimental LAC were determined using a NaI scintillation detector, the experimental results were compared with NIST-XCOM results, and a good agreement was noticed. The LAC values have been used to calculate some specific parameters, such as half value layer (HVL), mean free path (MFP), tenth value layer (TVL), and radiation protection efficiency (RPE), which are useful for discussing the shielding capabilities of gamma rays. The results of the shielding parameters show that the PP embedded with nBi2O3 gives better attenuation than its counterpart, PP embedded with mBi2O3, at all studied energies.