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Charles III arrived in Spain from Naples accompanied by a multidisciplinary team of military advisers, including Count Gazzola from Piacenza, who had already drawn up his plans for the urgent military reforms required for the artillery. These included the institutionalisation of that branch of the army and the foundation of the college for artillery officers and industrial engineers to run the military factories being taken over by the State. The most eye-catching element of this undertaking is the formation of its magnificent Enlightenment scientific library. A study of this library reveals an exceptional collection, the origins of the first books brought to the institution, the way it was organised and the military and scientific topics addressed. But its fundamental contribution can be measured in terms of results: indeed, textbooks were created for the cadets, as well as research works on military, artillery and scientific topics written by teachers from the college, and translations of important European scientific books. Finally, as a contribution to demonstrating the cost-effectiveness of the Crown’s investment in education for war, we highlight the work of three captains, showing the versatility they achieved thanks to their education at the college and their reputation outside it, in the service of society, as guiding lights of the Sociedad Económica de Amigos del País (SEAP – Economic Society of Friends of the Country) in Segovia. Without this magnificent library, the research, monographs and translations – ultimately the college’s own published works which brought it great academic credit in Enlightenment Europe – would not have been possible.