Face processing—a crucial social ability—is known to be carried out in multiple dedicated brain regions which form a distinguishable network. Previous studies on face processing mainly targeted the functionality of face-selective grey matter regions. Thus, it is still partly unknown how white matter structures within the face network underpins abilities in this domain. Furthermore, how relevant abilities modulate the relationship between face-selective and global fibers remains to be discovered. Here, we aimed to fill these gaps by exploring linear and non-linear associations between microstructural properties of brain fibers (namely fractional anisotropy, mean diffusivity, axial and radial diffusivity) and face processing ability. Using structural equation modeling, we found significant linear associations between specific properties of fibers in the face network and face processing ability in a young adult sample (N = 1025) of the Human Connectome Project. Furthermore, individual differences in the microstructural properties of the face processing brain system tended toward stronger differentiation from global brain fibers with increasing ability. This is especially the case in the low or high ability range. Overall, our study provides novel evidence for ability-dependent specialization of brain structure in the face network, which promotes a comprehensive understanding of face selectivity.
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