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We explored psychosocial pathways to longevity, specifically, the association between psychological well-being and mortality in a 20-year prospective cohort study of 7626 participants. As hypothesized, high self-acceptance and interdependence were associated with decreased mortality risk, controlling for other psychological components (purpose, positive relations, growth, mastery) and potential confounders: personality, depression, self-rated health, smoking status, body mass index (BMI), illness, and demographics. Self-acceptance decreased mortality risk by 19% and added three years of life. Longevity expectation fully mediated the relationship between self-acceptance and mortality. Interdependence decreased mortality risk by 17% and added two years of life. Serenity towards death fully mediated the relationship between interdependence and mortality. This is the first known study to investigate self-acceptance, interdependence, and serenity toward death as promoters of longevity, and distilled the relative contributions of these factors, controlling for covariates—all of which were measured over multiple time points. Theoretically, this study suggests that components of well-being may make meaningful contributions to longevity, and practically recommend that self-acceptance and interdependence could be added to interventions to promote aging health.