Media multitasking, or the concurrent consumption of multiple media forms, is increasingly prevalent in modern society and has been associated with decreased cognitive control abilities as well as negative psychosocial impacts such as depression and social anxiety, negative social well-being, and poor academic performance. While the cross-sectional nature of our study does not allow us to specify the direction of causality, our results brought to light novel associations between individual media multitasking behaviors and ACC structure differences. Our findings suggest a possible structural correlate for the observed decreased cognitive control performance and socio-emotional regulation in heavy media-multitaskers. Functional connectivity between this ACC region and the precuneus was negatively associated with MMI. This was confirmed via Voxel-Based Morphometry (VBM) analyses: Individuals with higher Media Multitasking Index (MMI) scores had smaller gray matter density in the anterior cingulate cortex (ACC). Thus, we expected differential engagements in media multitasking to correlate with brain structure variability. Research has demonstrated that brain structure can be altered upon prolonged exposure to novel environments and experience. The present study investigated relationships between media multitasking activity and brain structure. However, the neural processes associated with media multi-tasking remain unexplored. Individuals who engage in heavier media-multitasking are found to perform worse on cognitive control tasks and exhibit more socio-emotional difficulties. Media multitasking, or the concurrent consumption of multiple media forms, is increasingly prevalent in today’s society and has been associated with negative psychosocial and cognitive impacts.