He studied in the Colegio Mayor de Cuenca of the University of Salamanca and was professor of philosophy and rector of the institution.
He was enthroned in his cathedral on 2 January 1682 and one of his first acts was to found and build the Conciliar Seminary of Mexico – until then most priests serving in Mexican parishes were Spanish and had trained back in Spain itself.
A fifth trip (26 November 1687 – 24 January 1688) planned to reach Puerto de Acapulco, but he had to abandon it due to poor health.
Ascetic and moralistic, as archbishop he worked to ban cock-fighting, bull fighting, plays and secret theatre shows.
A group in Mexico started campaigning for his beatification straight after his death, with the support of archbishop Francisco de Lorenzana – the process began on 30 December 1767.