Age-related alterations in white matter have the potential to profoundly affect cognitive functioning. In fact, magnetic resonance imaging (MRI) studies using fractional anisotropy (FA) to measure white matter integrity reveal a positive correlation between FA and behavioral performance in older adults. Confounding these results are imaging studies demonstrating age-related white matter atrophy in some areas displaying altered FA, suggesting changes in diffusion may be simply an epiphenomenon of tissue loss. In the current study, structural MRI techniques were used to identify the relationship between white matter integrity and decreased volume in healthy aging adults. The data demonstrated that white matter atrophy did in fact account for differences in some areas, but significant FA decreases remained across much of the white matter after adjusting for atrophy. Results suggest a complex relationship between changes in white matter integrity and volume. FA appears to be more sensitive than volume loss to changes in normal appearing tissue, and these FA changes may actually precede white matter atrophy in some brain areas. As such, the ability to detect early white matter alterations may facilitate development of targeted treatments that prevent or slow age-related white matter degradation and associated cognitive sequelae.