In the last few decades, noninvasive neuroimaging has revealed macroscale brain dynamics that underlie perception, cognition, and action. Advances in noninvasive neuroimaging target two capabilities: 1) increased spatial and temporal resolution of measured neural activity; and 2) innovative methodologies to extract brain–behavior relationships from evolving neuroimaging technology. We target the second. Our novel methodology integrated three neuroimaging methodologies and elucidated expertise-dependent differences in functional (fused EEG-fMRI) and structural (dMRI) brain networks for a perception–action coupling task. A set of baseball players and controls performed a Go/No-Go task designed to mimic the situation of hitting a baseball. In the functional analysis, our novel fusion methodology identifies 50-ms windows with predictive EEG neural correlates of expertise and fuses these temporal windows with fMRI activity in a whole-brain 2-mm voxel analysis, revealing time-localized correlations of expertise at a spatial scale of millimeters. The spatiotemporal cascade of brain activity reflecting expertise differences begins as early as 200 ms after the pitch starts and lasts up to 700 ms afterwards. Network differences are spatially localized to include motor and visual processing areas, providing evidence for differences in perception–action coupling between the groups. Furthermore, an analysis of structural connectivity reveals that the players have significantly more connections between cerebellar and left frontal/motor regions, and many of the functional activation differences between the groups are located within structurally defined network modules that differentiate expertise. In short, our novel method illustrates how multimodal neuroimaging can provide specific macroscale insights into the functional and structural correlates of expertise development.