INAA (instrumental neutron activation analysis) was used to determine the contents of trace elements in coal samples from 11 workable Permian coal seams in Huainan coalfield. With XRFS (X-ray fluorescence spectrometry), the geochemical composition of its combustion residues from Tianjiaan Power Plant and Luohe Power Plant was analyzed. In addition, the electron microprobe was employed to study the chemical composition of some fly ashes and bottom ashes. Compared with those of the coals around the world, most trace elements of the Huainan coal are characterized by a normal abundance.Like most coals worldwide, the elements Se, S, As, Sb, Br, U and Cl are enriched in Huainan coal according to Clarks value, while the other elements tend to be diluted. The large fluctuation in the contents of trace elements in this kind of coal demonstrates great differences in coal seams. On the other hand, the contents of these elements are very similar in different bottom and fly ash samples. The elements with low organic affinity tend to concentrate in fly and bottom ash than in coal, especially those elements associated with Fe. However, the elements with strong organic affinity tend to be volatile during the combustion. Moreover, the abundance of the elements in fly ash and bottom ash changes with different densities and with different particle sizes. The bottom and fly ashes consist of glass, lime,mullite, coal residues and ferrite minerals. Some residual chars contain higher contents of volatile elements, such as S, P, Cl and As, indicating that the ash containing more residual chars has a strong adsorption of some hazardous elements, suggesting a possible utilization of power plant ash in the field of water cleaning.