Multiple learning systems allow individuals to flexibly respond to opportunities and challenges present in the environment. An evolutionarily conserved Pavlovian learning mechanism couples valence and action, promoting a tendency to approach cues associated with reward and to inhibit action in the face of anticipated punishment. Although this default response system may be adaptive, these hard-wired reactions can hinder the ability to learn flexible instrumental actions in pursuit of a goal. Such constraints on behavioral flexibility have been studied extensively in adults. However, the extent to which these valence-specific response tendencies bias instrumental learning across development remains poorly characterized. Here, we show that while Pavlovian response biases constrain flexible action learning in children and adults, these biases are attenuated in adolescents. This adolescent-specific reduction in Pavlovian bias may promote unbiased exploration of approach and avoidance responses, facilitating the discovery of rewarding behavior in the many novel contexts that adolescents encounter.