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Theories of network-based social capital and theories of social support have many conceptual overlaps yet few studies have examined the role of network structure in shaping functional elements of social support, emotional or instrumental. Utilizing the stress process model, this paper examines functional support as a mediator between ego-network structure—defined as density, efficiency, hierarchy, and constraint—and depressive symptoms and network structure as a moderator of support function on psychological distress. The results do not support a mediation process, rather, network structure moderates the effect of functional support on depressive symptomatology. In general, the findings suggest increased efficacy of social support when emotional networks have fewer structural holes and greater closure. However, high constraint shows a curvilinear relationship with moderate constraint being beneficial but depressive symptoms increasing as constraint increases toward high levels. These findings suggest that network structure alters the effect of perceived emotional support on depressive symptoms and that sociologists should more thoroughly examine formal social network structure as a predictor of mental health outcomes.