The motto of this work is to develop a flexible, lightweight metal-polymer composite for shielding diagnostic X-rays (40–140 kV) as an alternative to toxic lead/lead composite for making aprons, skirts, gonad shields, thyroid shield, etc. as they are effective in shielding ionizing radiations. But the uniform distribution of filler in the matrix is a major challenge. To overcome this drawback we have incorporated Bi2O3 in polyvinyl alcohol-polyvinyl pyrrolidone (PVA–PVP) blend by dissolving 0–5 gm of Bi2O3 in 4 molar HCl rather than dispersing nano/microparticles. More than 5 gm of Bi2O3 is not soluble in 4 molar HCl. Therefore, it is chosen as an optimum composition i.e. PB5. Bismuth oxide was found to react with HCl and form an amorphous BiOCl phase as validated by XRD and FT-IR. This amorphous phase was noticed to crystallize when sintered at 410 °C as confirmed through XRD. The X-ray attenuation characteristics were studied against accelerating voltage of 50-140 kV. The 5.5 mm thick PB5 sample shows the lead equivalent of 0.5 mm at 100 kV. It shows uniform attenuation throughout the matrix due to the uniform distribution of Bi as confirmed through EDX mapping. The PB5 composite has sufficient tensile strength, which is suitable for making radiation shielding apparel. [ABSTRACT FROM AUTHOR]