Humans can navigate through challenging environments (e.g., cluttered or uneven terrains) by modifying their preferred gait pattern (e.g., step length, step width, or speed). Growing behavioral and neuroimaging evidence suggests that the ability to modify preferred step patterns requires the recruitment of cognitive resources. In children, it is argued that prolonged development of complex gait is related to the ongoing development of involved brain regions, but this has not been directly investigated yet. Here, we aimed to elucidate the relationship between structural brain properties and complex gait in youth aged 9–18 years. We used volumetric analyses of cortical grey matter (GM) and whole-brain voxelwise statistical analyses of white matter (WM), and utilized a treadmill-based precision stepping task to investigate complex gait. Moreover, precision stepping was performed on step targets which were either unperturbed or perturbed (i.e., unexpectedly shifting to a new location). Our main findings revealed that larger unperturbed precision step error was associated with decreased WM microstructural organization of tracts that are particularly associated with attentional and visual processing functions. These results strengthen the hypothesis that precision stepping on unperturbed step targets is driven by cortical processes. In contrast, no significant correlations were found between perturbed precision stepping and cortical structures, indicating that other (neural) mechanisms may be more important for this type of stepping.