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Diocese in the province of Siena, in Tuscany. The city is built on the summit of Monte Poliziano. It is the ancient Etruscan city of Nocera Alfaterna, which in 308 B.C. made an alliance with Rome against the Samnites. In the Middle Ages it acknowledged the suzerainty of Florence, but was conquered by Siena in 1260. The cathedral was built in 1619, from plans by Scalzo; until the eighteenth century it held the tomb of Bartolomeo Arragazzi, secretary of Martin V, a work of Michelozzo. The church of the Madonna di San Biagio is a notable structure planned by Antonio da Sangallo (1518-37). The façades of the church of Saint Agostino and of the Oratorio della Misericordia are worthy of mention. Among the civic buildings are notable the Tarugi palace, like the Mercato a work of Pignola; the Contucci palace designed by Sangallo, and the fourteenth-century Palazzo Municipale, which contains a small gallery of Sienese and of Umbrian art. The most famous men of Montepulciano are Cardinal Bellarmine, Pope Marcellus II, Cervini, Angelo Ambrogini, better known as Poliziano (1454-1494), and the humanist Bartolomeo of Montepulciano. St. Agnes of Montepulciano died in 1137.

The city belonged originally to the Diocese of Arezzo, and had a collegiate church, whose archpriest became a mitred abbot in 1400; in 1480 it became a prælatura nullius , and in 1561 was made the seat of a bishop. Its first bishop was Spinello Benci (1562); among the others the following are well known: Talento de' Talenti (1640), a great savant; Antonio Cervini (1663), who did much for the cathedral and the episcopal palace; Pietro Francesi (1737) opposed the novelties of the Council of Florence in 1787; Pellegrino Maria Carletti (1802), author of several works and of eighteen letters on the National Council of Paris of 1810, at which he assisted. The diocese is immediately dependent on the Holy See , and has 18 parishes, 15,879 inhabitants, two religious houses of men, and two of women.

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