The main subject of this study is fly ash created during coal combustion in Rybnik Power Station in upper Silesia in the southern part of Poland. This is the biggest block power station in this region. Generated power is 1600 MW. Annual dust emission from professional energy in upper Silesia is estimated at 32.8 thousand tons, which is about 22% of total national emissions. X-ray powder diffraction, Analytic Scanning Electron Microscopy (ASEM) and Induced Couple Mass Spectrometry (ICP-MS) methods have been applied extensively to heavy metals (Cu, Ni, Pb, zn, Cr, Cd) content analysis and their host mineral phases identification. Concentrations of Cu, Ni, Pb, zn, Cr and Cd as well as mineral composition of fly ash being their carriers have been specified. Average zn concentrations in fly ash are 120 ppm, but for all other elements the averege concentrations were 38 ppm for Cu, 41 ppm for Ni, 44 ppm for Pb, 64 ppm for Cr and 3 ppm for Cd. Amorphic aluminosilicate substances, oxides and sulphides are mineral phases containing heavy metals. The sizes of these particles are up to 12 µm.