In 1685 he was elected bishop of Macerata and Tolentino, April 9, 1685, and later was appointed Nuncio in Cologne in 1696. Pope Innocent XII elevated him to the rank of cardinal in the consistory of 19 December 1698, and he became archbishop of Ferrara. He became Cardinal Secretary of State during the pontificate of Pope Clement XI. On Clement's death, at the succeeding conclave of 1721, Paolucci was the strongest candidate to succeed, but was vetoed by Charles VI, Holy Roman Emperor as he considered him too close to the French.
Pope Clement XI. On Clement
Paolucci