The neutron- and X-ray-shielding, morphological, physical, mechanical, and self-healing properties were investigated for natural rubber (NR) composites containing varying gadolinium oxide (Gd2O3) contents (0, 25, 50, 75, and 100 parts per hundred parts of rubber; phr) to investigate their potential uses as self-healing and flexible neutron- and X-ray-shielding materials. Gd2O3 was selected as a radiation protective filler in this work due to its preferable properties of having relatively high neutron absorption cross-section (σabs), atomic number (Z), and density (ρ) that could potentially enhance interaction probabilities with incident radiation. The results indicated that the overall neutron-shielding and X-ray-shielding properties of the NR composites were enhanced with the addition of Gd2O3, as evidenced by considerable reductions in the half-value layer (HVL) values of the samples containing 100 phr Gd2O3 to just 1.9 mm and 1.3 mm for thermal neutrons and 60 kV X-rays, respectively. Furthermore, the results revealed that, with the increase in Gd2O3 content, the mean values (± standard deviations) of the tensile strength and elongation at break of the NR composites decreased, whereas the hardness (Shore A) increased, for which extreme values were found in the sample with 100 phr Gd2O3 (3.34 ± 0.26 MPa, 411 ± 9%, and 50 ± 1, respectively). In order to determine the self-healing properties of the NR composites, the surfaces of the cut samples were gently pressed together, and they remained in contact for 60 min; then, the self-healing properties (the recoverable strength and the %Recovery) of the self-healed samples were measured, which were in the ranges of 0.30–0.40 MPa and 3.7–9.4%, respectively, for all the samples. These findings confirmed the ability to autonomously self-heal damaged surfaces through the generation of a reversible ionic supramolecular network. In summary, the outcomes from this work suggested that the developed Gd2O3/NR composites have great potential to be utilized as effective shielding materials, with additional dual shielding and self-healing capabilities that could prolong the lifetime of the materials, reduce the associated costs of repairing or replacing damaged equipment, and enhance the safety of all users and the public.