Silver played a key role in the progressive monetization of early Mediterranean civilizations. We combine Pb and Ag isotopes with volatile trace elements (Bi, Sb, and As) to assess whether, during the Roman occupation of Iberia, galena constituted a significant source of silver. We find that the Pb and Ag isotopic compositions of 47 samples of galena from eight different Iberian mining provinces, many of them exploited during Roman times, are uncorrelated. This indicates that their respective isotopic variabilities depend on different petrogenetic processes. Moreover, the range of Ag isotopic abundances is approximately six times wider than that displayed worldwide by silver coins in general and Roman silver coins in particular. Although galena from the Betics provides the best fit for Pb isotopes with Roman coins, their fit with Ag isotopic compositions is at best sporadic. We suggest that, together with Sb, Bi, and As, silver is primarily derived from fluids boiled off from differentiated mantle-derived magmas. These fluids, in turn, reacted with preexisting galena and functioned as a silver trap. Lead sulfides with ε109Ag of ~0 and unusually rich in Ag, Sb, Bi, and As were the most probable sources of ancient silver, whereas samples with ε109Ag departing significantly from ~0 reflect low-temperature isotopic fractionation processes in the upper crust.