The present study investigates associations between security of attachment in the mother-child relationship and patterns of brain connectivity in young adults. We hypothesized that secure attachment would relate to more efficient connectivity in white matter association fibers due to increased myelination. Attachment security was measured in 53 young adults using the Kerns Security Scale; anatomical information was acquired using diffusion tensor imaging. Higher fractional anisotropy, an index of directionality of diffusion, related to security of attachment in four left-hemisphere white matter association fibers (uncinate fasciculus, cingulum, superior longitudinal fasciculus, and inferior fronto-occipital fasciculus). As expected, this result was mainly ascribable to increased myelination, which has been independently associated with attachment security. Security of attachment may have an identifiable biological basis. Our research demonstrates the feasibility of coupling neuroimaging tools with clinical investigation.