The Antiquarium, a collection of archaeological artifacts discovered during various excavation campaigns since the end of the 19th century in the areas of Sant'Appiano, San Martino ai Colli, and Semifonte, is housed in the premises of the Pieve di Sant'Appiano in Barberino Val d'Elsa.

The first room houses a part of the funerary furnishings from numerous Etruscan tombs accidentally discovered in 1907 in the area of San Martino ai Colli by a local resident.

Among the most notable works is a "kelebe" (columned crater) with red figures from the 4th century BC and an alabaster urn from the Hellenistic period, with a relief of the Abduction of Proserpina and a lid decorated with a semi-reclining figure of a man.

In the second room, the most peculiar piece in the collection is a sandstone sculpture with a putto riding a dog, found during the late 19th-century excavations that also unearthed the foundations of the baptistery in front of the Pieve di Sant'Appiano.

The medieval and Renaissance periods are represented by a collection of ceramics found near Semifonte, the castle of the Alberti counts destroyed in 1202 by order of the city of Florence.

The only painting on display at the Antiquarium is a panel depicting the Madonna and Child with Saints John the Baptist and Anthony of Padua and two angels, painted by the Maestro di Signa, an anonymous artist from the first half of the 15th century.