Born in Polizzi Generosa, Sicily, Rampolla was the son of Ignazio Rampolla, Count of Tindaro, and of his wife, Orsola Errante. He is often referred to with the title of marquess, but this appears to be inaccurate. Rampolla was educated at the Collegio Capranica and the Pontifical Gregorian University. Having displayed a considerable knowledge in Oriental affairs, he was sent to the Pontifical Academy of Ecclesiastical Nobles as preparation for service in the Roman Curia.
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