Recently developed polymer-based composites could prove useful in many applications such as in radiation shielding. In this work, the potential of a bismuth oxide (Bi₂O₃) nanofiller based on an LDPE polymer was developed as lead-free X-ray radiation shielding offering the benefits of lightness, low-cost and non-toxic compared to pure lead. Three different LDPE-based composites were prepared with varying weight percentages of Bi₂O₃: 5%, 10% and 15%. The characterizations were extended to include structural properties, physical features, mechanical and thermal properties, and radiation shielding efficiency for the prepared nanocomposites. The results revealed that the incorporation of the Bi₂O₃ nanofiller into an LDPE improved the density of the composites. There was also a slight increase in the tensile strength and tensile modulus. In addition, there was a clear improvement in the efficiency of the shield when fillers were added to the LDPE polymer. The LDPE + Bi₂O₃ (15%) composite needed the lowest thickness to attenuate 50% of the incident X-rays. The LDPE + Bi₂O₃ (15%) polymer can also block around 80% of X-rays at 47.9 keV. In real practice, a thicker shield of the proposed composite materials, or a higher percentage of the filler could be employed to safely ensure the radiation is blocked.