The very pretty town of Montemerano was built and fortified in the 10th century by the ruling Aldobrandeschi family, founded by inhabitants fleeing coastal villages that were being repeatedly raided by Saracen pirates. A second larger city wall was built in the 12th and 13th centuries before the town was conqured by Orvieto, then the Republic of Siena. The medieval center, and especially the central Piazza del Castello public square, is particularly gorgeous.

Montemerano is also known for its fourteenth century parish church of San Giorgio and it prized artwork, especially the Madonna della Gattaiola painting – the Madonna of the Cat Flap – which, quite literally, is famous for having a small circular hole cut into it near the base. There are a couple of stories about it, but by far the best one is that it was cut by the resident priest to allow his cat to enter the church to hunt for mice!