Many scholars have argued that more equal patterns of landownership, as well as the supremacy of industry over agriculture, have been found to be associated with the rise of mass public education systems in the late-eighteenth and early-nineteenth centuries. The theoretical background behind this argument mainly relies on the so-called capital-skill complementarity hypothesis, which states that agricultural land and industrial capital were characterized by different levels of complementarity with human skills. Thus, on the one hand, large landowning elites were often reluctant to promote and support mass public education, while, on the other hand, rising capitalists have been much more favoured by a better-educated workforce, promoting major educational reforms. The present paper attempts to provide some of the first evidence for the existence of a positive relationship between people’s access to land and literacy development in the late nineteenth-century Greece based on data collected from the 1870 and 1879 Greek Population Censuses. Our empirical estimates largely confirm previous findings in the literature, indicating a positive and significant linkage between people’s access to land and literacy rates. On the contrary, stuck in agriculture has been found to be negatively related to literacy expansion. These results remain robust even after controlling for various other factors, such as marital status, family size, sex ratio, urbanization, ethnicity and religion.