Links among concurrent and longitudinal changes in pubertal development and empathic ability from ages 10 to 13 and neural responses while witnessing peer rejection at age 13 were examined in 16 participants. More advanced pubertal development at age 13, and greater longitudinal increases in pubertal development, related to increased activity in regions underlying cognitive aspects of empathy. Likewise, at age 13 greater perspective taking related to activity in cognitive empathy‐related regions; however, affective components of empathy (empathic concern and personal distress) were associated with activity in both cognitive and affective pain‐related regions. Longitudinal increases in empathic ability related to cognitive and affective empathy‐related circuitry. Findings provide preliminary evidence that physical and cognitive‐emotional development relate to adolescents' neural responses when witnessing peer rejection.