Socioeconomic status is an important predictor of cognitive development and academic achievement. Late adolescence provides a unique opportunity to study how the attainment of socioeconomic status (in the form of years of education) relates to cognitive and neural development, during a time when age‐related cognitive and neural development is ongoing. During late adolescence it is possible to disambiguate age‐ and education‐related effects on the development of these processes. Here we assessed the degree to which higher educational attainment was related to performance on a cognitive control task, controlling for age. We then used diffusion tensor imaging (DTI) to assess the degree to which white matter microstructure might mediate this relationship. When covarying age, significant associations were found between educational attainment and fractional anisotropy (FA) in the superior longitudinal fasciculus (SLF) and cingulum bundle (CB). Further, when covarying age, FA in these regions was associated with cognitive control. Finally, mediation analyses revealed that the age‐independent association between educational attainment and cognitive control was completely accounted for by FA in these regions. The uncinate fasciculus, a late‐myelinated control region not implicated in cognitive control, did not mediate this effect. Socioeconomic status is an important predictor of cognitive development and academic achievement. Late adolescence provides a unique opportunity to study how the attainment of socioeconomic status (in the form of years of education) relates to cognitive and neural development, during a time when age‐related cognitive and neural development is ongoing. During late adolescence it is possible to disambiguate age‐ and education‐related effects on the development of these processes.