Due to rapid increases in the utilization of radiation and nuclear technologies, effective and suitable radiation-shielding materials have become one of the most sought-after options to protect users and the public from excessive exposure to the radiation. However, most radiation-shielding materials have greatly reduced mechanical properties after the addition of fillers, resulting in their limited useability and shortened lifetime. Therefore, this work aimed to alleviate such drawbacks/limitations by exploring a possible method to simultaneously enhance both the X-ray shielding and mechanical properties of bismuth oxide (Bi2O3)/natural rubber (NR) composites through multi-layered structures, with varying (1–5) layers and a total combined thickness of 10 mm. To correctly determine the effects of the multi-layered structures on the properties of NR composites, the formulation and layer configuration for all multi-layered samples were tailored such that their theoretical X-ray shielding properties were equal to those of a single-layered sample that contained 200 phr Bi2O3. The results indicated that the multi-layered Bi2O3/NR composites with neat NR sheets on both outer layers (sample-D, sample-F, sample-H, and sample-I) had noticeably higher tensile strength and elongation at break than those of the other designs. Furthermore, all multi-layered samples (sample-B to sample-I), regardless of the layer structure, had enhanced X-ray shielding properties compared to those with a single layer (sample-A), as shown by their higher values of the linear attenuation coefficient (µ) and lead equivalence (Pbeq) and the lower value of the half-value layer (HVL) in the former. This work also determined the effects of thermal aging on relevant properties for all samples, with the results revealing that all the thermal-aged composites had higher values for the tensile modulus but lower values for the swelling percentage, tensile strength, and elongation at break, compared with the non-aged composites. Hence, based on the overall outcomes from this work, it could be concluded that the worrisome decreases in mechanical properties of the common single-layered NR composites after the addition of Bi2O3could be prevented/reduced by introducing appropriate multi-layered structures, which would not only widen potential applications but also prolong the lifetime of the composites.