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Education is a fundamental cause of social inequalities in health because it influences the distribution of resources, including money, knowledge, power, prestige, and beneficial social connections, that can be used in situ to influence health. Recent studies have highlighted early-life cognition as commonly indicating the propensity for educational attainment and determining health and age of mortality. Health behaviors provide a plausible mechanism linking both education and cognition to later-life health and mortality. We examine the role of education and cognition in predicting smoking, heavy drinking, and physical inactivity at midlife using data from the Wisconsin Longitudinal Study (N = 10,317), National Survey of Health and Development (N = 5,362), and National Childhood Development Study (N = 16,782). Adolescent cognition was associated with education but was inconsistently associated with health behaviors. Education, however, was robustly associated with improved health behaviors after adjusting for cognition. Analyses highlight structural inequalities over individual capabilities when studying health behaviors.