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This article provides the first harmonized quantitative evidence on the rise of mass education across the provinces (today’s NUTS 3) of Italy and Spain in the period c. 1861–1921. Visual analysis of this new dataset suggests that an important factor linked to the expansion of schooling was the feminization of the teaching profession, something that has been largely neglected so far in quantitative historical studies of educational development. This hypothesis is put to the test using panel-data models. The results show that the feminization of teaching went hand in hand with the rise of schooling rates by prompting more girls to enrol into primary education. By the beginning of the twentieth century, Italy’s gross enrolment rate had surpassed that of Spain—partly as the result of increasing feminization within the primary-school teaching profession.