The purpose of this paper is to assess the content and distribution of some elements in coal from two bituminous coal basins and in fly ash and slag derived from combustion of the coals in six power plants in Poland. The petrographic composition and distribution of elements were characterized in the tested samples, using reflected light microscope, X-ray powder diffractometer, inductively coupled plasma atomic emission spectroscopy, and scanning electron microscope with energy dispersive X-ray. The highest content of elements in coal occurs in siderite. In Al-Si particles, as well as in magnetite with skeletal and dendritic structure crystallized on the surface of Al-Si microspheres or cenospheres included in fly ash size < 0.05 mm and in the magnetic fraction of slag, the highest content of elements was noted. Due to the content of elements, fly ash and slag were considered to be neutral for the soil environment. Correlations, which have not been described before, have been observed between the likely mode of binding of some elements in coal and their distribution in fly ash and slag. These correlations could be of particular value when predicting the content and distribution of elements in combustion residues and in the assessment of their environmental toxicity.