Background: Augmentation index (AIx) and pulse wave velocity (PWV) are early markers of atherosclerotic vascular changes and also have been shown to be predictive of cardiovascular disease and total mortality. The aim of our study was to evaluate the relationship between PWV and AIx-HR75, which is the corrected form of AIx according to a heart rate of 75 beats/min, echocardiographic parameters and biochemical parameters in chronic hemodialysis (HD) patients. Subjects and methods: AIx-HR75 and PWV were measured in 556 HD patients by applanation tonometry using the SphygmoCor device. Results: The mean PWV and AIx-HR75 values of the study group were 10.2 ± 2.4 and 28.4 ± 10.2 m/s. A positive correlation was found between PWV and AIx-HR75 (r = 0.214, p = 0.000). AIx-HR75 correlated with age (r = 0.093, p = 0.028), body surface area (BSA) (r = −0.194, p = 0.000), mean arterial pressure (MAP) (r = 0.335, p = 0.000), pulse pressure (PP) (r = 0.212, p = 0.000), cardiothoracic index (r = 0.155, p = 0.016), and presence of left ventricular hypertrophy (r = 0.152, p = 0.001). PWV correlated with MAP (r = 0.208, p = 0.000), PP (r = 0.098, r = 0.021), left ventricular mass (r = 0.105, p = 0.023), and predialysis sodium level (r = −0.105, p = 0.023). In the multivariate analyses, PWV was associated with MAP (t = 3.78, p = 0.000), presence of diabetes (t = 3.20, p = 0.001), and predialysis sodium level (t = −2.06, p = 0.040), and AIx-HR75 was associated with age (t = 2.48, p = 0.014), female sex (t = 3.98, p = 0.000), BSA (t = −2.15, p = 0.033), and MAP (t = 7.02, p = 0.000). Conclusion: There is a strong association between MAP and arterial stiffness parameters in HD patients. We feel that efficient control of blood pressure could lead to reduced arterial stiffness in HD patients.