St Alban’s English College in Valladolid, established at the height of the Catholic Reformation for the training of English secular clergy under the rule of Spanish Jesuits, underwent an alteration in its management after the expulsion of the religious order from Spain in 1767. As part of this process, numerous valuable archival records were produced which have not, thus far, been studied. This article analyses a portion of these documents: the surviving manuscript inventories of the library. It also considers the series of governmental orders issued by the Spanish authorities as part of the process of expulsion and examines how these orders shaped the production of the library inventories. It offers an overview of the contents of the catalogues, with descriptions of some of those specific book entries that make these inventories unique. The study of these archival documents provides insight into, and understanding of, a key moment in the College history: its shift from Spanish Jesuit control to an English secular one and the difficulties that the Spanish authorities faced because of this change in the College’s national identity.