Tuscany represents one of the most important ancient mining districts of Italy. Metalworking activities have been present in the area since ancient times and several mining centres have been active in the region since the Etruscan period. Two of the more notable mining locations are the island of Elba and the towns of Populonia and Massa Marittima.In order to reconstruct the development of metallurgical techniques in the past, a multi-disciplinary approach is required, involving both archaeological study and archaeometric analysis of the sites of interest. One of the most complex problems is establishing the chronological history of metallurgical exploitation in ancient sites: archaeological remains are sometimes incomplete and the stratigraphy of archaeological horizons might have been deeply altered. Thus, direct dating of metallurgical slags and other remains of mining and metalworking activities using radiocarbon measurements is particularly useful for developing site chronologies.Charcoal samples from a recent excavation in Populonia were dated by AMS radiocarbon in order to reconstruct the chronological evolution of ancient metallurgical production; results reported here are consistent with archaeological observations.