The mobility of inorganic pollutants is of key concern for a range of industrial and engineering applications of fly ash produced during the combustion of lignite in power generation. This paper investigates the role that the geochemical features of lignite, the ash composition and the partitioning of elements during combustion play in determining leaching properties of lignite fired by-products. The work is based on surveys on three lignite-fired power plants in Greece. Calcium-rich ashes show a high abatement potential for SO2 and other gaseous pollutants. For most elements, the concentrations in the parent lignite and the ashes follow the same trend. Relative enrichments in Cd, Co, Cr, Cu, Mo, Ni, Pb, U, V, W, Zn fingerprint the regional and local geological settings of the lignite basins. The total and leachable concentrations of highly volatile elements are strongly influenced by the interaction with ubiquitous free lime. A broad array of elements is highly insoluble in alkaline ash, while a few oxyanionic-forming elements display substantial mobility. Their mode of occurrence in the parent lignite plays a primary role in the leaching of combustion ashes. The outcomes of this study may assist in addressing the impact of co-firing high ash or high Ca alternative fuels on the leaching properties of combustion by-products.