In this study, we investigated a novel polymer nano-composite, PS-PbO, containing two distinct nano-sizes of lead oxide nanoparticles (PbO-A and PbO-B), in addition to the bulk size (PbO-K). These nanoparticles were embedded separately in a polystyrene (PS) matrix at different weight percentages (10%, 15%, 25%, and 35%) using roll mill mixing and compressing molding. Our evaluation focused on the radiation attenuation ability of PS-PbO and the effect of particle size, considering gamma-ray energies ranging from 0.06 to 1.3 MeV (from sources like 241Am, 133Ba, 137Cs, and 60Co). The linear attenuation coefficient (LAC) was determined by analyzing samples of the synthesized composite with different thicknesses. Then, various shielding parameters were calculated, including total molecular, atomic, and electronic cross-sections (σmol, σatm, σel), as well as the effective atomic number and the electron density (Zeff and Neff). Surprisingly, modifying PbO particle sizes had a significant impact on shielding efficiency. For instance, the composite with 25 wt% of the smallest PbO-B particles showed a 26.7% increase in LAC at 0.059 keV compared to the composite with 25 wt% of PbO-K (larger particles). Notably, the LAC peaked at low energy (0.059 keV), close to the K-edge of Pb, where interaction is directly proportional to Z4. With increasing PbO concentrations, the LAC of PS-PbO composites increased steadily. Additionally, as PbO concentration increased, the composite’s effective atomic number Zeff and the electron density Neff increased, leading to a greater total Gamma-ray interaction cross-section. Furthermore, when comparing the Half-Value Layers of the novel nanocomposite to traditional lead shielding, a 70% reduction in mass was observed. Notably, the composite containing the smallest nano-size of PbO exhibited the highest radiation-shielding efficiency among all combinations and could therefore be used to create inexpensive and lightweight shields.