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Atherosclerosis is a leading cause of death. To better understand and treat this disease, it is important to evaluate the changes in blood vessel wall microstructure during disease development and to link these structural changes to changes in mechanical properties. Microfocus X-ray computed tomography (microCT) is a powerful technique for assessing, in a non-invasive way, the 3D microstructure of complex materials. To achieve sufficient X-ray attenuation in soft tissues, contrast-enhancing staining agents (CESAs) containing high atomic number molecules are combined with microCT. This technique is referred to as contrast-enhanced microCT (CE-CT). Monolacunary and Hafnium-substituted Wells-Dawson polyoxometalate(Mono-WD and Hf-WD POM respectively) have shown their potential for non-destructive staining of kidney and soft skeletal tissues [1]. Additionally, we have shown with planar biaxial testing that these POMs have a negligible effect on the mechanical properties of the tissue. In this study, both CESAs were evaluated and compared for their staining potential of the porcine aorta. Other types of blood vessels were imaged to show the ability of CE-CT to highlight the vessel wall microstructure, including the different wall layers and their content in elastin and collagen. The novelty of this study lies in the high-detailed comparison of the microstructure of different types of blood vessels(healthy and diseased) in a non-invasive way.