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Archaeometric investigation allowed the characterization of two important classes of ceramics: ‘vetrina sparsa’ and ‘invetriata grezza’. Their archaeological peculiarity makes them particularly suited for tracing the evolution of glaze manufacturing in southern Tuscany throughout the medieval period (10th–14th centuries). These ceramics were found in different sites of historical importance, and also from a mining perspective. Local copper, lead, zinc and iron mineralizations supported the growth of several settlements in the vicinity of the mines. The many castles and different archaeological finds (ceramics, glazed ceramic, slag etc.) attest to the intense mineral exploitation of the area from at least the first millenniumbc up to the modern period. In light of these geological and archaeological characteristics, archaeometric investigation was intended to provide insight into ancient technical knowledge of ceramic glazing and to determine the source area for raw materials in the medieval period (10th–14th centuries). Ceramic bodies were analysed through OM, XRDp, SEM–EDS and XRF, while coatings were investigated through SEM–EDS. Mineralogical, petrographic and chemical analyses revealed slightly different preparation and firing processes for the two classes of ceramics. These data suggest the continuity through the centuries of the ‘vetrina sparsa’ and ‘invetriata grezza’ production technology. The mineralogical phases, such as monazite, xenotime, zircon, barite, Ti oxide, ilmenite, titanite, tourmaline and ilvaite, and the lithic (intrusive and volcanic) fragments detected within the ceramic bodies suggest a source area in the vicinity of the Campiglia mining district. Lastly, the presence of Cu–Zn–Pb (Ag) and Fe sulphide mineralizations (materials used to produce glaze) in the area supports the hypothesis of local manufacture. [ABSTRACT FROM AUTHOR]