Aortic pulse wave velocity (PWV) has been accepted as the gold standard for arterial stiffness measurement. However, PWV depends on blood pressure (BP). To eliminate the BP dependency of PWV, the cardio–ankle vascular index (CAVI) was developed. This study aimed to define the relationship between CAVI and aortic atherosclerosis or structure on multidetector computed tomography (MDCT). Patients with (n = 49) or without (n = 49) coronary artery disease were studied. The lumen and vessel diameters and wall thickness were calculated from the cross-sectional area at the pulmonary bifurcation level by 64-slice MDCT. The CAVI was measured within 3 days before MDCT. Multivariate analysis showed that the vessel diameter of the ascending and descending aorta on MDCT depends on age, body surface area, and diastolic BP. The CAVI significantly correlated with the vessel diameter (r = .453) and wall thickness (r = .387) of the thoracic descending aorta (P < .001, respectively). The CAVI was an independent predictor of the descending aortic wall thickness on multiple stepwise regression analysis. These data suggest that CAVI, a simple index, is useful for evaluating thoracic aortic atherosclerosis.