Coal fly ash in the atmosphere affects air quality and potentially influences the global climate by promoting oceanic productivity. Although accurately tracing the sources of fly ashes is vital for emission control, it remains a challenging task. Stable lead (Pb) isotope analysis is a useful tool for tracing atmospheric pollution but it fails to accurately address coal combustion emissions due to the broad range of Pb isotopic composition of coal. Environmental magnetic parameters can be used as a rapid and economical proxy for tracing atmospheric pollutants (including coal fly ashes) and have the potential for discriminating emission sources. In this study, we combined magnetic parameters with Pb isotopic signatures in order to better discriminate the sources of coal fly ash. Both magnetic particles and Pb are highly concentrated in the fly ashes compared with the feed coals. Most of the fly ashes exhibit higher Pb/Pb and lower Pb/Pb ratios than those of the feed coals. Furthermore, the Pb isotopic compositions of the fly ashes are highly correlated (p < 0.01) with the concentrations of magnetic particles (especially hematite), suggesting that the variation of Pb isotopes in the fly ashes is controlled by the adsorption of Pb on magnetic minerals. Based on the established relationship between magnetic minerals and Pb isotopes within coal fly ashes, we re-analyzed previously reported magnetic and Pb isotopic data from atmospheric dust and demonstrated the effectiveness of the combined method in discriminating coal fly ash in the atmosphere.