American adolescents currently live in a variety of different family structures, with the vast majority of adolescents living in intact, blended, divorced, and never-married families. Previous research shows that family structure correlates both with the quality of parent–adolescent relationships and adolescent psychological distress. The quality of parent–adolescent relationships also correlates with adolescent distress. This research hypothesizes that the observed differences in adolescent distress across family structure might result from differences in the quality of parent–adolescent relationships across family structure. Analyses, using data on 1,443 youth in early and middle adolescence from the National Longitudinal Survey of Youth (NLSY), indicate that when the variations in both the quality of parent–adolescent relationships and background characteristics across family structure are controlled, the association between family structure and adolescent psychological distress is significantly reduced. Further analyses revealed that the quality of residential parent–adolescent relationships explained the most variation in adolescent psychological distress. The quality of relationships with nonresidential fathers only had a significant association with adolescent psychological distress for adolescents in blended families.