Background: The purpose of the study is to evaluate the association between cognitive function and risk of all-cause and cardiovascular disease mortality during 10 years of the follow-up. Methods: 7087 participants were assessed in the baseline survey of the Health Alcohol Psychosocial Factors in Eastern Europe (HAPIEE) study in 2006–2008. During 10 years of follow-up, all-cause and CVD mortality risk were evaluated. Results: During 10 years of follow-up, 768 (23%) men and 403 (11%) women died (239 and 107 from CVD). After adjustment for sociodemographic, biological, lifestyle factors, and illnesses, a decrease per 1 standard deviation in different cognitive function scores increased risk for all-cause mortality (by 13%–24% in men, and 17%–33% in women) and CVD mortality (by 19%–32% in men, and 69%–91% in women). Kaplan-Meier survival curves for all-cause and CVD mortality, according to tertiles of cognitive function, revealed that the lowest cognitive function (1st tertile) predicts shorter survival compared to second and third tertiles (p < 0.001). Conclusions: The findings of this follow-up study suggest that older participants with lower cognitive functions have an increased risk for all-cause and CVD mortality compared to older participants with a higher level of cognitive function.