Disparities in children’s expressive language by socio-economic status are evident early in childhood and impact children’s development and educational attainment. This study investigated the processes by which maternal education, as a powerful indicator for socio-economic status, affects early expressive language. A nationally representative cohort study of 8,062 children resident in the Republic of Ireland were assessed on the British Ability Scales (BAS) Naming Vocabulary Test at 36 months. A significant difference of almost six points was found between the mean vocabulary test scores of children whose mothers had completed the minimum level of educational attainment compared with children whose mothers had a degree-level qualification. Mediation analysis revealed that 78% of the difference was explained by mediating variables, with differences in household income, parental practice, and material resources accounting for most of the variation. The findings support interventions which redress gaps in maternal education, income, and caregiving.