We compared psychological resources between heterosexual never-married and married adults and their group-specific role in positive and negative affect after controlling for social resources. Although never-married respondents scored slightly lower than married adults on social resources and affective well-being, the two groups were comparable on psychological resources. Moderated regression analysis indicated that psychological resources were more strongly related to negative affect for never-married than married adults. In addition, never-married respondents with lower personal mastery scored higher on negative affect than did married adults, and higher levels of self-sufficiency contributed to lower negative affect for never-married adults but to higher negative affect among married individuals. Psychological resources appear to have a differential role in shaping negative affect between never-married and married individuals.