We addressed the relationship between white matter architecture, represented by MRI fractional anisotropy (FA), and cognition in individuals with first-episode psychosis (FEP) by applying for a new methodology that allows whole brain parcellation of core and peripheral white matter in a biologically meaningful fashion. Regionally specific correlations were found in FEP between three specific domains of cognition (processing speed, attention/working memory, and executive functioning) and FA at the deep (cerebral peduncles, sagittal striatum, uncinate, internal/external capsule, cingulum) and peripheral white matter (adjacent to inferior temporal, angular, supramarginal, insula, occipital, rectus gyrus).