Prosocial behavior plays an important role in establishing and maintaining relationships with others and thus may have important developmental implications. This study examines the association between cortical thickness and prosocial behavior in a population-based sample of 6- to 9-year-old children. The present study was embedded within the Generation R Study. Magnetic resonance scans were acquired from 464 children whose parents had completed the prosocial scale of the Strengths and Difficulties Questionnaire. To study the association between cortical thickness and prosocial behavior, we performed whole-brain surface-based analyses. Prosocial behavior was related to a thicker cortex in a cluster that covers part of the left superior frontal and rostral middle frontal cortex (p < .001). Gender moderated the association between prosocial behavior and cortical thickness in a cluster including the right rostral middle frontal and superior frontal cortex (p < .001) as well as in a cluster covering the right superior parietal cortex, cuneus, and precuneus (p < .001). Our results suggest that prosocial behavior is associated with cortical thickness in regions related to theory of mind (superior frontal cortex, rostral middle frontal cortex cuneus, and precuneus) and inhibitory control (superior frontal and rostral middle frontal cortex).