Cardiovascular disease (CVD) and osteoporosis are major causes of morbidity and mortality in postmenopausal women. The relationship between atherosclerosis and osteoporosis has been established by studies of the underlying pathophysiological mechanisms and biochemical pathways that seem to overlap in many places. Pulse wave velocity (PWV) is one of the known predictors of cardiovascular and all-cause mortality. Studies indicate that PWV in hypertensive postmenopausal women is increased, and hormone replacement therapy (HRT) attenuates this increase. In addition, recently, many studies have suggested a role for arterial stiffness in the association between CVD and osteoporosis. From these findings, it appears that estrogen deficiency combined with production of inflammatory cytokines plays a role in increased PWV closely associated with CVD and osteoporosis, although the mechanisms of arterial stiffness in postmenopausal women may be more complex. Accordingly, a possible role for PWV as a surrogate marker of CVD as well as osteoporosis in postmenopausal women is discussed in this review. First, menopause leads to increased arterial stiffness with aging in females. Further, epidemiological data evaluating arterial stiffness assessed by PWV provided evidence that most of the established CVD risk factors are determinants of PWV, and these risk factors are increased in patients with CVD. In turn, contrary to expectation, HRT did not always contribute to a lower incidence of CVD in postmenopausal women. By reviewing the current data available, it becomes clear that, at present, the effects of menopause including HRT on PWV remain controversial, and further studies are needed to clarify these associations.