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Background There is strong evidence that vascular dysfunction is considered one of the possible causes of morbidity and mortality in patients suffering from multiple sclerosis (MS). This work aimed at assessing the arterial function and serum lipids in MS patients and correlating them with clinical and radiological findings. Results This case–control study included 50 patients with MS and 50 age- and sex-matched controls. The arterial function was significantly reduced in MS patients, confirmed by significantly higher pulse wave velocity (PWV) and augmentation index (AIX), while the carotid IMT did not show significant difference between the two groups with no plaques in any of our patients. A significant positive correlation was found between PWV and both disease duration and disability. MS patients had significantly higher serum levels of T-cholesterol and triglycerides, and significantly lower serum levels of HDL-cholesterol, compared to controls. No significant correlation was found between serum lipids and either disease duration or disability. Conclusions There was a significant impairment in arterial function (assessed by the brachial cuff-based method via Mobil-O-Graph device) in MS patients compared to controls. Such impairment was significantly correlated with both disease duration and disability. MS patients had also significantly higher levels of T-cholesterol and triglycerides, compared to controls with no significant correlation between serum lipids and either disease duration or disability.