In 1724 he was named by pope Benedict XIII Bishop of Arezzo where a diocesan synod was celebrated in 1730 under his leadership.
He was born in Gravina in Puglia to Ferdinando III Orsini, duke of Gravina, and Giovanna Frangipani della Tolfa, from Toritto.
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Benedict died in 1730 and was buried in a tomb in Santa Maria sopra Minerva completed by Pietro Bracci and others.
The city is named for Stanisław Kostka, a Polish priest who was canonized by Pope Benedict XIII on November 13, 1726, 23 years before San Estanislao was founded.
With the authorisation of Pope Benedict XIII, the bishopric's lands were being sold to the local inhabitants as independent municipalities, to pay for the successive wars in which Spain had been involved.
In 1727, Benedict XIII founded the Universitas Studii Generalis with the faculties of theology, jurisprudence, medicine, and mathematics.
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In the 17th Century Pope Benedict XIII beatified Angelo Carletti, giving official approval to the cult that had for long been paid to Angelo, especially by the people of Chivasso and Coni.
In 1729 Pope Benedict XIII inscribed his liturgical feast day in the Roman Calendar for 12 June, since 11 June, the anniversary of his death was occupied by the feast of Saint Barnabas.
On 20 September 1415, the Emperor met with Pope Benedict XIII at the palace with the King Ferdinand I of Aragon and the delegations of the Counts of Foix, Provence, Savoy, Lorraine, the embassy of the Roman church for the Council of Constance, and embassies from the Kings of France, England, Hungary, Castille and Navarre.