Cognitive conflict detection and resolution develops with age across childhood and likely supports age-related increases in other aspects of cognitive and emotional development. Little is known about the neural correlates of conflict detection and resolution in early childhood. In the current study, we investigated age-related change in neural recruitment during a blocked spatial-incompatibility task (Simon task) in children ages 5–10 years using fMRI. Cortical thickness was measured using structural MRI. Across all children, there was greater activation in right prefrontal and bilateral parietal cortices for incompatible than compatible conditions. In older children, compared with younger children, there was decreased activation and decreased gray matter thickness in the medial PFC. Thickness and activation changes across age were associated within participants, such that thinner cortex was associated with less activation in the rostral ACC. These findings suggest that developmental change in medial PFC activation supports performance on cognitive control tasks in early childhood.