As Archbishop of Milan he focused on pastoral activities, taking as examples Saint Charles Borromeo and Pope Innocent XI.
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He was appointed Titular archbishop of Thessalonica on 18 December 1711, and shortly after consecrated bishop in Rome by Cardinal Fabrizio Paolucci.
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His great uncle was Pope Innocent XI, who died when Benedetto was 10 and from whom in 1709 Benedetto took his second surname Odescalchi.
Benedetto Croce | Erba | Benedetto Bordone | Livio Odescalchi | Erba (CO) | Caslino d'Erba | Benedetto Luti | San Benedetto del Tronto | Portico e San Benedetto | Benedetto Castelli | Villa Erba | San Benedetto dei Marsi | San Benedetto | Odescalchi | John Benedetto | Italian battleship Benedetto Brin | Giovanni Benedetto Platti | Darío Benedetto | Conservatorio di Musica Benedetto Marcello di Venezia | Castello Orsini-Odescalchi | Benedetto Varchi | Benedetto Possenti | Benedetto Pamphili | Benedetto Gennari | Benedetto Brin | ''Benedetto Brin'' |