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There has been a rapid increase in studies using diffusion-weighted magnetic resonance imaging (DWI) to interrogate white matter structure in the human brain. This review considers the evidence that interindividual variation in white matter structure is behaviourally relevant.Maturation or deterioration of white matter throughout the lifespan relates to development or decline in specific cognitive skills. In addition, age-independent relationships between white matter anatomy and ability are found in healthy adult populations. Such relationships may in part be determined by genetics but can also be driven by experience.Individual differences in white matter anatomy, visible using DWI, have consequences for behaviour. The discovery of such relationships highlights the potential for identification of imaging biomarkers that could predict how well patients will respond to specific interventions.