Introduction Cognitive impairment is a major, but underdiagnosed, risk factor for negative outcomes in patients with chronic kidney disease (CKD). The main goal of this study was to evaluate, for the first time, the relationship between arterial stiffness and cognitive impairment in a cohort of hemodialysis patients. Methods We prospectively analyzed the cognitive function and pulse wave velocity (PWV) of 72 hemodialysis patients, mean age 56.54 ± 13.96 y, from two Romanian dialysis centers. We administered to all patients the Mini Mental State Examination (MMSE), Trail Making Test Part-A (TMTA) and Part-B (TMTB), and Mini-Cog Test. Radial arterial waveforms during 40 cardiac cycles were recorded in each patient. Findings Mean MMSE score was 25.13 ± 3.47, mean MiniCog score was 3.51 ± 1.18, mean TMTA (sec) was 103.77 ± 53.13 and mean TMTB (sec) was 214.93 ± 112.25. In linear unadjusted regression, PWV values were associated with worse MMSE scores (β = -0.36, P = 0.001, 95% CI: -0.68 to -0.17), and MiniCog scores (β = -0.26, P = 0.02, 95% CI: -0.19 to -0.01). Also, PWV value was significant associated with TMTA test, but not with TMTB. After further adjustments, PWV remained a strong predictor for cognitive impairment measured by MMSE, TMTA, MiniCog, but not for TMTB. Discussion Cognitive impairment was associated with higher PWV values in our cohort. Further evidence is needed in order to support arterial stiffness as a long-term predictor for cognitive decline in ESRD patients.