Severe acute exacerbations of chronic obstructive pulmonary disease (AECOPD) are associated with significant poor outcomes including an increased risk of cardiovascular (CV) events and exercise intolerance. Endothelial dysfunction might contribute to an impaired vascular homeostasis and consequently to CV events and exercise capacity. This study aimed to evaluate the association between exercise capacity and endothelial function in patients with severe AECOPD. Forty-five COPD patients diagnosed with severe AECOPD and admitted to the University Hospital of São Carlos from 2017 to 2019 were enrolled in this observational clinical study. Endothelial Function was assessed by brachial artery ultrasonography (M-Turbo, Sonosite, Bottle, WA, USA) and Flow Mediated Dilatation (FMD) technique in absolute (mm) and percentage values (%). Walking distance (6MWD) obtained by six-minute walk test was considered to characterize the exercise capacity. Pearson’s correlation analysis and linear regression model were applied and a significance level of 5%. There was a significant positive correlation between exercise capacity and endothelial function. Pearson correlation coefficient were 0.36 (p = 0.02) and 0.40 (p = 0.01) between 6MWD and FMD in mm and %, respectively. Linear regression model revealed 6MWD (p = 0.007), accounting for 15% of FMD (%) variance (R2 adjusted). FMD (%) = 2.11 + (0.0081*6MWD). Exercise capacity is associated with endothelial function in patients with severe AECOPD. FMD was found to be increasing with increasing walked distance. Further research is needed to provide evidence of effectiveness of rehabilitation on exercise capacity and endothelial function in these patients and its prognostic value.