To overcome the severe toxicity and blind absorption zone of conventional lead-based shielding materials for X-rays in the 70-90 keV range, the lead-free multilayered polymer composites were designed and fabricated. The effects of the direction of incidence of the X-rays and number of layers as well as layer thickness ratio of the (tungsten/ethylene-octene copolymer)/(bismuth/ethylene-octene copolymer) layered composites on their shielding efficiency were studied systematically. Compared to the traditional polymer blending, the multilayered polymer composites exhibited the improved photon attenuation. The multilayered polymer composites (layer thickness ratio was 3:7) with 6 layers had the best X-ray shielding ability. Moreover, the X-ray shielding provided by the multi-layered interfaces and the multiple complementary effect of the absorption within the multilayered structure were firstly proposed based on computer simulations. The multilayered structural design effectively weakened the probability of the X-ray penetration. Therefore, the X-ray shielding capability can be effectively enhanced through increasing number of layers and the synergistic effect of multi-layered interfaces. The experimental results of this study can serve as guidelines for the fabrication of flexibility, lead-free, lightweight and high-efficiency X-ray shielding materials.