The reduced risk of dementia in high-educated individuals has been suggested to reflect brain reserve capacity. In the present study, we determined the association between integrity of white matter microstructure and education separately in twenty-one patients with clinically probable Alzheimer's disease (AD) and 18 healthy elderly subjects. We used fractional anisotropy derived from high-resolution diffusion-tensor weighted imaging at 3 Tesla as an in vivo marker of white matter microstructure. Based on multivariate network analysis, more years of education were associated with reduced white matter integrity of medial temporal lobe areas and association fiber tracts when age, gender, and dementia severity had been controlled for (p < 0.001). In controls, higher education was associated with greater white matter integrity in medial temporal lobe areas and association fiber tracts (p < 0.001). In multiple regression models, education was the main factor accounting for fiber tract integrity even when occupation was taken into account. Reduced fiber tract integrity with higher education at the same level of cognitive impairment in AD patients and higher fiber tract integrity with higher education in similar white matter areas in cognitively healthy controls agrees with the hypothesis that white matter microstructure may contribute to brain reserve capacity in humans.