Past studies have linked differences in white matter tissue properties to reading skills. However, these studies have reported a range of, sometimes conflicting, results. Some studies suggest that white matter properties act as individual-level traits predictive of reading skill, whereas others suggest that reading skill and white matter develop as a function of an individual's educational context. In the present study, we tested two hypotheses: a) that diffusion properties of the white matter reflect stable brain characteristics that relate to reading skills over development or b) that white matter plays a part in a dynamic system, linked with learning over time. To answer these questions, we examined the relationship between white matter and reading in a series of large-scale, single-observation datasets and a four-year longitudinal dataset. We find that gains in reading skill correspond to longitudinal changes in the white matter. However, in the single-observation datasets, we find no evidence for the hypothesis that individual differences in white matter predict reading skill. These findings highlight the link between dynamic processes in the white matter and learning.