During adolescence, prefrontal cortex regions, important in cognitive control, undergo maturation to adapt to changing environmental demands. Ways through which social-ecological factors contribute to adolescent neural cognitive control have not been thoroughly examined. We hypothesize that household chaos is a context that may modulate the associations among parental control, adolescent neural cognitive control, and developmental changes in social competence. The sample involved 167 adolescents (ages 13–14 at Time 1, 53% male). Parental control and household chaos were measured using adolescents’ questionnaire data, and cognitive control was assessed via behavioral performance and brain imaging at Time 1. Adolescent social competence was reported by adolescents at Time 1 and at Time 2 (one year later). Structural equation modeling analyses indicated that higher parental control predicted better neural cognitive control only among adolescents living in low-chaos households. The association between poor neural cognitive control at Time 1 and social competence at Time 2 (after controlling for social competence at Time 1) was significant only among adolescents living in high-chaos households. Household chaos may undermine the positive association of parental control with adolescent neural cognitive control and exacerbate the detrimental association of poor neural cognitive control with disrupted social competence development.