Polymer composites were synthesized via melt mixing for radiation shielding in the healthcare sector. A polymethyl-methacrylate (PMMA) matrix was filled with Bi2O3nanoparticles at 10%, 20%, 30%, and 40% weight percentages. The characterization of nanocomposites included their morphological, structural, and thermal properties, achieved using SEM, XRD, and TGA, respectively. The shielding properties for all synthesized samples including pristine PMMA were measured with gamma spectrometry using a NaI (Tl) scintillator detector spanning a wide range of energies and using different radioisotopes, namely Am-241 (59.6 keV), Co-57 (122.2 keV), Ra-226 (242.0), Ba-133 (80.99 and 356.02 keV), Cs-137 (661.6 keV), and Co-60 (1173.2 and 1332.5 keV). A substantial increase in the mass attenuation coefficients was obtained at low and medium energies as the filler weight percentage increased, with minor variations at higher gamma energies (1173 and 1332 keV). The mass attenuation coefficient decreased with increasing energy except under 122 keV gamma rays due to the K-absorption edge of bismuth (90.5 keV). At 40% loading of Bi2O3,the mass attenuation coefficient for the cesium137Cs gamma line at 662 keV reached the corresponding value for the toxic heavy element lead. The synthesized PMMA-Bi2O3nanocomposites proved to be highly effective, lead-free, safe, and lightweight shielding materials for X- and gamma rays within a wide energy range (<59 keV to 1332 keV), making them of interest for healthcare applications.