This study explored the neural correlates of emotion regulation and emotional reactivity in early to mid‐childhood. A sample of 96 children (70% White, mid‐to‐high socioeconomic status) aged 3–8 years provided structural neuroimaging data and caregivers reported on emotion regulation and emotional reactivity. The amygdala, insula, inferior frontal gyrus, anterior cingulate cortex, and medial orbitofrontal cortex were explored as a priori regions of interest (ROIs). ROI analyses revealed that emotion regulation was positively associated with cortical thickness in the insula, whereas emotional reactivity was negatively associated with cortical thickness in the inferior frontal gyrus. Exploratory whole‐brain analyses suggested positive associations between emotion regulation and both left superior temporal thickness and right inferior temporal thickness, as well as negative associations between emotional reactivity and left superior temporal thickness. There were no significant associations between emotional regulation or reactivity and amygdala volume or cortical surface area. These findings support the notion that surface area and cortical thickness are distinct measures of brain maturation. In sum, these findings suggest that children may rely on a wider set of neural regions for emotion regulation and reactivity than adults, which is consistent with theories of interactive specialization across the life span.