Emission inventories indicate that thallium, a highly toxic metal, is emitted during coal burning and cement production. These estimates have been established only for the 1980s and 1990s but up to now they have not been compared to long-term observations. Here we used alpine ice cores to document thallium pollution over Europe since ∼1850. Ice-core thallium concentrations increased from 1890 to 1910, and decreased after 1965 to concentrations that were half 1890 levels. Comparison of ice-core trends, estimated past emissions, and state-of-the-art atmospheric aerosol transport modeling suggest that coal burning was responsible for thallium pollution in Europe, particularly from 1920 to 1965 because of high coal consumption at that time. The subsequent decline resulted from decreased coal consumption and reduced emissions following technological improvements. The ice-core data suggest that the rapid growth of cement production that took place in Europe after 1950 had a limited impact on thallium pollution.