This report addresses a way to reduce the usage of highly toxic lead in diagnostic X-ray shielding by developing a cost-effective, eco-friendly nano-tungsten trioxide (WO3) epoxy composite for low-weight aprons. Zinc (Zn)-doped WO3 nanoparticles of 20 to 400 nm were synthesized by an inexpensive and scalable chemical acid–precipitation method. The prepared nanoparticles were subjected to X-ray diffraction, Raman spectroscopy, UV-visible spectroscopy, photoluminescence, high-resolution–transmission electron microscope, scanning electron microscope, and the results showed that doping plays a critical role in influencing the physico-chemical properties. The prepared nanoparticles were used as shielding material in this study, which were dispersed in a non-water soluble durable epoxy resin polymer matrix and the dispersed materials were coated over a rexine cloth using the drop-casting method. The X-ray shielding performance was evaluated by estimating the linear attenuation coefficient (μ), mass attenuation coefficient (μm), half value layer (HVL), and X-ray percentage of attenuation. Overall, an improvement in X-ray attenuation in the range of 40–100 kVp was observed for the undoped WO3 nanoparticles and Zn-doped WO3 nanoparticles, which was nearly equal to lead oxide-based aprons (reference material). At 40 kVp, the percentage of attenuation of 2% Zn doped WO3 was 97% which was better than that of other prepared aprons. This study proves that 2% Zn doped WO3 epoxy composite yields a better particle size distribution, μm, and lower HVL value and hence it can be a convenient lead free X-ray shielding apron.