Relationships between maternal education (ME) and both behavioral performances and brain activation during the discrimination of phonemic and nonphonemic sounds were examined using fMRI in children with different levels of phoneme categorization proficiency (CP). Significant relationships were found between ME and intellectual functioning and vocabulary, with a trend for phonological awareness. A significant interaction between CP and ME was seen for nonverbal reasoning abilities. In addition, fMRI analyses revealed a significant interaction between CP and ME for phonemic discrimination in left prefrontal cortex. Thus, ME was associated with differential patterns of both neuropsychological performance and brain activation contingent on the level of CP. These results highlight the importance of examining SES effects at different proficiency levels. The pattern of results may suggest the presence of neurobiological differences in the children with low CP that affect the nature of relationships with ME.