The potential utilization of wood/polyvinyl chloride (WPVC) composites containing an X-ray protective filler, namely bismuth oxide (Bi2O3) particles, was investigated as novel, safe, and environmentally friendly X-ray shielding materials. The wood and Bi2O3 contents used in this work varied from 20 to 40 parts per hundred parts of PVC by weight (pph) and from 0 to 25, 50, 75, and 100 pph, respectively. The study considered X-ray shielding, mechanical, density, water absorption, and morphological properties. The results showed that the overall X-ray shielding parameters, namely the linear attenuation coefficient (µ), mass attenuation coefficient (µm), and lead equivalent thickness (Pbeq), of the WPVC composites increased with increasing Bi2O3 contents but slightly decreased at higher wood contents (40 pph). Furthermore, comparative Pbeq values between the wood/PVC composites and similar commercial X-ray shielding boards indicated that the recommended Bi2O3 contents for the 20 pph (40 ph) wood/PVC composites were 35, 85, and 40 pph (40, 100, and 45 pph) for the attenuation of 60, 100, and 150-kV X-rays, respectively. In addition, the increased Bi2O3 contents in the WPVC composites enhanced the Izod impact strength, hardness (Shore D), and density, but reduced water absorption. On the other hand, the increased wood contents increased the impact strength, hardness (Shore D), and water absorption but lowered the density of the composites. The overall results suggested that the developed WPVC composites had great potential to be used as effective X-ray shielding materials with Bi2O3 acting as a suitable X-ray protective filler.