Author Summary Network control theory suggests that the functions of large-scale brain circuits can be partially described with respect to the ability of brain regions to steer brain activity to different states. This ability, often quantified in terms of controllability metrics, has normally been derived from the structural architecture of the white matter fiber tracts. However, gray matter as the substrate that engenders much of the neural processes is widely ignored in this context. In the present work, we study the relationship between regional gray matter volume and control properties across the whole cortex and provide evidence that control properties not only depend on the connection strength of the structural connectome but also depend on sufficient gray matter volume at the host nodes. Abstract Brain controllability properties are normally derived from the white matter fiber tracts in which the neural substrate of the actual energy consumption, namely the gray matter, has been widely ignored. Here, we study the relationship between gray matter volume of regions across the whole cortex and their respective control properties derived from the structural architecture of the white matter fiber tracts. The data suggests that the ability of white fiber tracts to exhibit control at specific nodes not only depends on the connection strength of the structural connectome but additionally depends on gray matter volume at the host nodes. Our data indicate that connectivity strength and gray matter volume interact with respect to the brain’s control properties. Disentangling effects of the regional gray matter volume and connectivity strength, we found that frontal and sensory areas play crucial roles in controllability. Together these results suggest that structural and regional properties of the white matter and gray matter provide complementary information in studying the control properties of the intrinsic structural and functional architecture of the brain.