A historical centre of Semproniano is gathered on a travertine base of 662 m above sea level.

Around the X century, the strong boundary wall was built around the small nucleon of Casale Simprunianum. Initially dominated by the Aldobrandeschi, then around 1200 this small community got under the dominion of Contea of S. Fiora. After the attack of the Sienese army (1300), it became a part of the Republic of Siena. It was a buffer zone between Siena and the Orsini of Pitigliano. In 1411, during a battle between the two adversaries, Sienese set fire on the walls of Semproniano. The whole village was hit badly. The republic of Siena, disapproving of the dreadful action, sought to help the village with special measures. The population decided to definitely hunt the Orsini. In the XVI century, Semproniano passed to the Medici and in 1737 became part of the Grand Duchy of Tuscany. The community regained its independence in 1963 with the reconstruction of the Comune of Semproniano.

The ancient unit, with tight and tortuous roads was developed in semicircles around the Aldobrandescan Fortress. There is not much left of the fortress, however the panoramic view at Mt. Amiata is worth the trip. There is no doubt that Casale Simprunianum had occupied the area where later on the Aldobrandescan fotress was built. Sideways of the fortress, on the square, there is the Church of Holy Cross (Chiesa di Santa Croce). The first historical mention dates back to the Pop's bull of Clemente III in 1188. Unfortunately, the church had experienced the same destiny as the fortress did. Its actual appearance is very simple; there is an arc in the middle of it. The walls are painted in black and white (the colors of Siena). To the right from the main door, there is a holy-water font in travertine, made out of a tube and a column of '500 and of a base shaped as an animal's three-fingers foot which dates back to more ancient period. Above the altar, there is a wooden Crucifix of the XII century, some parts of which were renewed in '700. A miracle had been attributed to this cross that was supposed to happen on May 3, 1882. When the village was suffering from typhus, the desperate believers had taken the cross to the procession and suddenly the illness disappeared. On the opposite wall, there is a painting of Veneto school '700 that represents the Compassion.

Going down towards the village, we find Piazzoletta, a social centre of an ancient village. There is the Palazzo Civico on the square from which, unfortunately, only some portals in its interior have remained. In front, there is a tiny street that in ancient times was connecting the centre with the Church of St. Vincenzo. Around 1565, there was probably the residence of a vicar of the Medici under the arc. (This assumption is supported by the Florentine fleur-de-lis engraved on one stony portal).
Taking the stairs down, we arrive in via San Francesco, where there are some traces of ancient portals and sculpted windows. We can admire a window of the '400 and a monogram on the lintel situated on the birth house of Bishop Banci. Following this street, we finally arrive at Pieve dei SS. Vincenzo e Anastasio, known for its Romanic-gothic portal. It was remembered in 1274 and remained as the parochial seat until 1969. Three large stone arches support the roof. On the southern wall there are two Roman-gothic windows, while on the northern one there are sculpted stones and an epigraph that remembers the restoration of 1579. It has undergone several restorations until the last one, which succeeded to return its original appearance. Of interest is the holy-water font in travertine of the X century, as well as the baptismal font attributed to the XIII century. Furthermore, five paintings have been preserved, three of which are attributed to the school of Gerolamo del Pacchia (dated back to the II half of '500) representing the Virgin with the Child among the Saints, Vincenzo and Anastasio, San Mamiliano and San Rocco. The remaining two are of late '600 or '700 and recall the legend of a monster, and the other one the crusade of the Rosary. The temple was consecrated in 1844, as demonstrated in an epigraph in the interior of the Tower Campanario. The tower is the most ancient of the entire territory. It is 23 m high and its original appearance was changed following the restorations.
Leaving from the ancient country we can visit the oratory of San Rocco, raised around '400. There is a renaissance arc to be found on its facade.