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Recent demographic findings show increased rates of death due to suicide, drug addictions, and alcoholism among midlife white adults of lower socioeconomic status (SES). These have been described as “deaths of despair” though little research has directly assessed psychological vulnerabilities. This study used longitudinal data from the Midlife in the U.S. (MIDUS) study to investigate whether low levels of eudaimonic and hedonic well-being predict increased risk of deaths of despair compared to other leading causes of death (cancer, heart disease). The investigation focused on 695 reported deaths with cause of death information obtained from 2004 to 2022 via NDI Plus. Key questions were whether risk for deaths due to despair (suicide, drug addiction, alcoholism) compared to deaths due to cancer or heart disease were differentially predicted by deficiencies in well-being, after adjusting for sociodemographic variables. Low levels of purpose in life, positive relations with others, personal growth and positive affect predicted significantly greater likelihood of deaths of despair compared to deaths due to heart disease, with such patterns prominent among better-educated adults. The findings bring attention to ongoing intervention efforts to improve psychological well-being.