Background: CKD is a significant cause of morbidity, cardiovascular and all-cause mortality. CHA2DS2-VASc is a score used in patients with atrial fibrillation to predict thromboembolic risk; it also appears to be useful to predict mortality risk. The aim of the study was to evaluate CHA2DS2-VASc scores as a tool for predicting one-year mortality after hemodialysis is started and for identifying factors associated with higher mortality. Methods: Retrospective analysis of patients who started hemodialysis between January 2014 and December 2019 in Centro Hospitalar Universitário Lisboa Norte. We evaluated mortality within one year of hemodialysis initiation. The CHA2DS2-VASc score was calculated at the start of hemodialysis. Results: Of 856 patients analyzed, their mean age was 68.3 ± 15.5 years and the majority were male (61.1%) and Caucasian (84.5%). Mortality within one-year after starting hemodialysis was 17.8% (n = 152). The CHA2DS2-VASc score was significantly higher (4.4 ± 1.7 vs. 3.5 ± 1.8, p < 0.001) in patients who died and satisfactorily predicted the one-year risk of mortality (AUC 0.646, 95% CI 0.6–0.7, p < 0.001), with a sensitivity of 71.7%, a specificity of 49.1%, a positive predictive value of 23.9% and a negative predictive value of 89.2%. In the multivariate analysis, CHA2DS2-VASc ≥3.5 (adjusted HR 2.24 95% CI (1.48–3.37), p < 0.001) and central venous catheter at dialysis initiation (adjusted HR 3.06 95% CI (1.93–4.85)) were significant predictors of one-year mortality. Conclusion: A CHA2DS2-VASc score ≥3.5 and central venous catheter at hemodialysis initiation were predictors of one-year mortality, allowing for risk stratification in hemodialysis patients.