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Refereed/Peer-reviewed Adolescence is a critical period of social and neural development. Brain regions which process social information develop throughout adolescence as young people learn to navigate social environments. Studies investigating brain structural connectivity (indexed by white matter (WM) integrity), and social connectedness in adolescents have been limited until recently, with literature stemming mostly from adult samples, broad age ranges within adolescence or based on social network characteristics as opposed to social connectedness. This cross-sectional study of 12-year-olds (N = 73) explored the relationship between social connectedness (SCS) and structural connectivity in early adolescence, to gauge how this snapshot of WM development is associated with social behaviour. Whole brain voxel-wise diffusion tensor imaging was undertaken to determine correlations between SCS and fractional anisotropy (FA), radial (RD) and axial (AD) diffusivity of clusters within WM tracts. Significant negative relationships between FA and SCS scores were found in clusters within 11 WM tracts, with significant positive correlations between SCS and both RD and AD across clusters within 13 and 8 clusters, respectively. Clusters within the genu of the corpus callosum (CCgn) showed strong correlations for all three metrics, and regression models that included gender, age, and psychological distress, revealed SCS to be the only significant predictor of CCgn FA, RD and AD values. Overall, these findings suggest that those with lower social connectedness had a WM profile suggestive of reduced axonal density and/or coherence. Longitudinal research is needed to track such WM profiles during adolescent development and determine the associations with mental health and well-being outcomes.