Early language exposure and shared parent–child reading, as assessed by maternal reading ability and fluency, affect the child’s future language and cognitive abilities. The aim of the current study was to explore the association between maternal reading ability and fluency and diffusion properties of language- and cognition-related white matter tracts in their pre-school age children using diffusion tensor imaging (DTI). DTI data were acquired from fifteen girls (mean age: 3.83 ± 0.49 years). Reading ability and fluency were assessed in their mothers. Effects of hemisphere and node on diffusion properties were measured at 100 points along white matter tracts related to language and cognitive abilities. Significant positive correlations were found between maternal reading ability and fractional anisotropy in left and right dorsal and ventral language and executive functions-related tracts, while maternal reading fluency was associated with higher fractional anisotropy in ventral tracts, mainly in the left hemisphere. Fractional Anisotropy was significantly higher in the left compared to the right arcuate, cingulum cingulate, and inferior longitudinal fasciculus and higher in the right compared to the left superior longitudinal fasciculus. Our results signify the importance of maternal reading as a facilitator of the child’s future language and cognitive abilities.