The silver–sulpharsenide vein deposits of Cobalt, Ontario, crosscut basement Archean metavolcanic rocks, Proterozoic strata, and younger Proterozoic diabase sills. A petrographic and sulphur-isotope study of the metallic minerals was initiated to assess possible genetic models of vein formation. Discrete differences exist between the sulphur-isotope compositions of basement sulphides (δ34S = + 4.0‰), brecciated wall-rock sulphides (+ 3.5‰), and vein sulphides (+ 2.3‰). The δ34S values consistently increase with distance from the vein centres. Sulphur-isotope fractionation trends are similar for all the vein deposits studied. Sulphur-isotope data suggest that sulphides were deposited between 130 and 254 °C. Based on the assumption of equilibrium between chalcopyrite and galena, the initial δ34S of the fluid was between + 5.0 and + 11.0‰. The release of sulphur during the reaction of Archean pyrite with Proterozoic formational brines to form pyrrhotite is proposed to explain the heavy sulphur isotopic composition of the fluid. This process could also have provided the Ni, Co, and As, known to be concentrated in some pyrite, that was deposited in the silver veins. Interpretation of mineral paragenesis and geothermometry indicate that temperature decreased and aS2 increased as deposition proceeded.