Natural leather (NL) based composite protection materials with lightweight, flexibility, wearability and high shielding efficiency will remarkably innovate the current research on X-ray protection materials. A co-doped Bi/Ce-NL composite with outstanding X-ray attenuation in the energy range of 20-120 keV is successfully fabricated. The uniform distribution of BiO and CeO nanoparticles in the hierarchical structure of natural leather significantly promotes the X-ray attenuation by improving the weak absorption region of Bi with Ce via synergistic effects of the two elements. The fabricated Bi/Ce-NL loading with 0.755 mmol cm BiO and 1.51 mmol cm CeO achieves approximately 100% X-ray shielding when the energy below 40 keV. Thus, the fabricated Bi/Ce-NL with superb X-ray attenuation can safely and comfortably protect human from the risk of X-ray exposure with low bulk density, high water vapor permeability, exceptional mechanical properties and excellent bending resistance, presenting significant advantages in wearability and flexibility compared to both traditional lead-based and polymer-based protection materials.