Novel, flexible, lead-free X-ray-shielding composites were prepared with a high-functional methyl vinyl silicone rubber (VMQ) matrix with W and Bi 2 O 3 as filler materials. To verify the advanced properties of the lead-free material, composites with the same mass fraction of PbO were compared. With the X-ray energy ranging from 48 to 185 keV, the W/Bi 2 O 3 /VMQ composites exhibited higher X-ray-shielding properties. As the filler volume fraction decreased, the tensile strength, elongation, tear strength, and flexibility of the W/Bi 2 O 3 /VMQ composites increased. The Shore hardness of the W/Bi 2 O 3 /VMQ composites had a maximum value of 46.6 HA and was still very flexible. With decreasing filler volume fraction, the water-vapor transmission performances of the W/ Bi 2 O 3 /VMQ composites increased, and the W/Bi 2 O 3 /VMQ composites also showed better water-vapor permeability. The heat-transfer properties of the W/Bi 2 O 3 /VMQ composites increased with increasing W content, and when the W content exceeded 70 wt %, the thermal conductivity of the W/Bi 2 O 3 /VMQ material was about 70.45% higher than that of the PbO/VMQ composite. V C 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43012.