Few studies have evaluated neuroanatomical differences between illiterates and literates and majority have been unimodal investigations. We explore multiparametric, neuroanatomical substrates of literacy by studying grey and white matter microstructural neuroimaging biomarker differences between 61 literate and 15 illiterate elderly subjects with normal cognition. Univariate and multivariate methods for grey matter density, diffusion tensor parameters and cortical/subcortical morphometric measures were employed. Literacy provided an advantage through increase in grey matter density, white matter integrity, cortical thickness, area and volumes in brain areas related to reading, writing, language, Visuospatial and sensorimotor processes. Enhanced white matter integrity was the most discriminating factor on the machine learning.