This paper reports on results from a multi-sampling campaign (stack, fugitive emissions and ambient air measurements) to characterise the geochemical signature of metal and metalloid particles emitted from one of the largest Cu-smelters in the world (in Huelva, SW Spain). Exceptionally high concentrations of very fine particles (<0.33 μm) bearing As, Cd, Pb, Cu, Bi, Zn (∑>100 μg m−3) are emitted from the Flash Smelting Furnaces, but high levels are also emitted by the other main chimney stacks, namely Refining Furnaces, Sulphuric Plant, Converters Unit, and Crushing Plant. Enhanced concentrations of the same elements are also observed in ground measurements near the industrial complex. During the sampling campaign, the presence of plumes from the Cu-smelter over the nearby city of Huelva was identified based on increased concentrations of gaseous pollutants, particulate metals and ultrafine particle numbers (PN). The results demonstrate that the Cu-smelter is an important source of inhalable toxic elements carried by fine airborne particles. The pollution abatement systems applied so far appear to be relatively ineffective in preventing metalliferous air pollution events, potentially increasing health risks to local and regional populations.