Although the development of executive functions has been extensively investigated at a neurofunctional level, studies of the structural relationships between executive functions and brain anatomy are still scarce. Based on our previous meta-analysis of functional neuroimaging studies examining executive functions in children (Houdé, Rossi, Lubin, and Joliot, (2010). Developmental Science, 13, 876–885), we investigated six a priori regions of interest: the left anterior insular cortex (AIC), the left and the right supplementary motor areas, the right middle and superior frontal gyri, and the left precentral gyrus. Structural magnetic resonance imaging scans were acquired from 22 to 10-year-old children. Local gray matter volumes, assessed automatically using a standard voxel-based morphometry approach, were correlated with executive and storage working memory capacities evaluated using backward and forward digit span tasks, respectively. We found an association between smaller gray matter volume – i.e., an index of neural maturation – in the left AIC and high backward memory span while gray matter volumes in the a priori selected regions of interest were not linked with forward memory span. These results were corroborated by a whole-brain a priori free analysis that revealed a significant negative correlation in the frontal and prefrontal regions, including the left AIC, with the backward memory span, and in the right inferior parietal lobe, with the forward memory span. Taken together, these results suggest a distinct and specific association between regional gray matter volume and the executive component vs. the storage component of working memory. Moreover, they support a key role for the AIC in the executive network of children.