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Adolescents' peer culture plays a key role in the development and maintenance of risk-taking behavior. Despite recent advances in developmental neuroscience suggesting that peers may increase neural sensitivity to rewards, we know relatively little about how the quality of peer relations impact adolescent risk taking. In the current 2-year three-wave longitudinal study, we examined how chronic levels of peer conflict relate to risk taking behaviorally and neurally, and whether this is modified by high-quality peer relationships. Forty-six adolescents completed daily diaries assessing peer conflict across 2 years as well as a measure of peer support. During a functional brain scan, adolescents completed a risk-taking task. Behaviorally, peer conflict was associated with greater risk-taking behavior, especially for adolescents reporting low peer support. High levels of peer support buffered this association. At the neural level, peer conflict was associated with greater activation in the striatum and insula, especially among adolescents reporting low peer support, whereas this association was buffered for adolescents reporting high peer support. Results are consistent with the stress-buffering model of social relationships and underscore the importance of the quality of adolescents’ peer relationships for their risk taking.