In this article, the archaeological and archaeometrical study of several roof tiles and bricks retrieved at the Etruscan Domus dei Dolia is presented. The Domus is located in Etrusco-Roman neighbourhood (Hellenistic – Late Republican periods, third–first centuries BC) of the ancient city of Vetulonia (central Italy), in the area of Poggiarello Renzetti. The main goals were to establish the characteristics of the raw material/s used in their production, the possible provenance, the technology applied, and to get insight regarding the production organization and the local economy. The archaeological materials were analysed by optical microscopy (OM), X-ray diffraction (XRD), and X-ray fluorescence (XRF). Principal component analysis was also applied to evaluate/interpret chemical data. Results evidenced that roof tiles and bricks were produced using a different technology and raw materials. Roof tiles were possibly manufactured within 12 km from the archaeological site and imported into the town, exploiting two different raw materials. Conversely, bricks were likely produced very close to the archaeological site. So, it is supposed that raw materials were selected considering factors such as distance, abundance, and accessibility to natural resources and security.