Background: Cardiovascular mortality is extremely high in patients on hemodialysis. Among a variety of pathophysiological conditions, deranged calcium homeostasis including secondary hyperparathyroidism may be one of the factors contributing to cardiovascular disease in patients on hemodialysis. This study was designed to evaluate the role of the serum parathyroid hormone (PTH) concentration and its regulatory factors in serum on arterial stiffness in patients on maintenance hemodialysis. Methods: Arterial stiffness was assessed by pulse wave velocity (PWV) in 73 non-diabetic patients undergoing maintenance hemodialysis. At the same time, serum concentrations of calcium, phosphate, and intact PTH were measured. Results: Single regression analyses revealed that arterial PWV was positively correlated with age (r = 0.505, p < 0.0001), systolic blood pressure (r = 0.250, p = 0.043), and pulse pressure (r = 0.306, p = 0.012). It was inversely correlated with the serum phosphate concentration (r = –0.240, p = 0.041) and the duration of hemodialysis treatment (r = –0.343, p = 0.003), but not with serum concentrations of calcium and intact PTH or the calcium × phosphate product in serum. By multiple regression analysis age was found to be the most significant variable affecting arterial PWV, and the duration of hemodialysis treatment negatively influenced arterial PWV. Conclusion: Age is an independent risk factor for arterial stiffness in patients on maintenance hemodialysis, and the serum PTH concentration and its regulatory factors in the serum are not.