The mineralogy, petrography and major- and trace-element composition of iron ores from Elba Island (Tuscany, Italy), one of the most important iron sources in the Mediterranean area since the first millennium bc, revealed that hematite-rich ores display prominent enrichments in W and Sn (up to 4950 μg g−1 and 8400 μg g−1, respectively). These two elements are hosted by tiny grains of W–Sn mineral phases (ferberite, scheelite and cassiterite) that are disseminated throughout the hematite matrix. A comparison with iron ores from many Italian and European localities (most of which were exploited in ancient times) suggests the uniqueness of the geochemical pattern of Elba Island hematite-rich ores (i.e., high W and Sn, low Mo and low Cu, Pb and Zn). We suggest that this geochemical signature may represent a new provenance marker not only for discarded ore at smelting/smithing sites, but, possibly, also for metallurgical slag and smelted metal produced in the chaîne opératoire of the iron process.