Background Pulse wave velocity (PWV) is a noninvasive measure of arterial stiffness and predictor of cardiovascular disease. However, the association between PWV and vascular calcification across different vascular beds has not been fully investigated. This study aimed to quantify the association between PWV and multiterritory calcification and to explore whether PWV can identify individuals with vascular calcification beyond traditional risk factors. Methods and Results Among 1351 older adults (mean age, 79.2 years [SD, 4.1]) from the ARIC (Atherosclerosis Risk in Communities) study, we measured segment‐specific PWVs: heart–carotid, heart–femoral, carotid–femoral, heart–ankle, brachial–ankle, and femoral–ankle. Dependent variables were high calcium score (≥75th percentile of Agatston score) across different vascular beds: coronary arteries, aortic valve ring, aortic valve, mitral valve, ascending aorta, and descending aorta. Quartiles of carotid–femoral, heart–femoral, heart–ankle, and brachial–ankle PWV were significantly associated with coronary artery calcium (eg, adjusted odds ratio [OR] for the highest versus lowest quartile of carotid–femoral PWV, 1.84 [95% CI, 1.24–2.74]). Overall, PWVs were most strongly associated with descending aorta calcification, with significant results for carotid–femoral, heart–femoral, heart–ankle, and brachial–ankle PWV (eg, adjusted OR for the highest versus lowest quartile of carotid–femoral PWV, 3.99 [95% CI, 2.61–6.17]). In contrast, femoral–ankle PWV was inversely associated with descending aorta calcification. Some PWVs improved the discrimination of coronary artery calcium and descending aorta calcification beyond traditional risk factors. Conclusions The associations of PWV with vascular calcification varied substantially across segments, with descending aorta calcification most closely linked to PWVs. Our study suggests that some PWVs, especially carotid–femoral PWV, are helpful to identify individuals with coronary artery calcium and descending aorta calcification.