How much and why individuals in romantic relationships drink alcohol may be a function of both personal and relational influences. The current research examined factors that predict vulnerability to health-related risky behavior (i.e., drinking to cope and drinking problems) in response to relationship difficulties. We consider the possibility that for individuals whose self-worth is contingently tied to the fluctuations of their relationship, feeling less satisfied may predict increased drinking problems; moreover, this may be mediated by drinking to cope. This study evaluated relationship-contingent self-esteem (RCSE) as a moderator of the association between relationship satisfaction and coping motives, which was expected to predict alcohol problems in couples. Both members in committed relationships (N = 78 dyads) reported relationship satisfaction, RCSE, drinking to cope motives, and alcohol problems in a cross-sectional survey. Actor–Partner Interdependence Model analyses revealed significant mediated moderation among men, such that higher RCSE interacted with lower relationship satisfaction to predict stronger coping motives, in turn predicting increased drinking problems. Implications and future directions are discussed.