The Kozani-Ptolemais-Amyntaio basin constitutes the principal coal field of Greece. Approximately 50% of the total power of Greece is generated by five power stations operating in the area. Pulverized lignite, a bottom ash, and a fly ash sample from the power plant of Amyntaio were subjected to a leaching procedure. The relative mass leached (RML) of three potentially toxic trace elements (Cu, Cr, Ni) was determined by use of AAS. Results indicate that the determined elements are more readily available in fly ash than in bottom ash or pulverized lignite. Mineralogical examination of the samples has revealed that calcite, gypsum, quartz, and feldspar are the constituents of lignite; quartz and calcite are found in fly ash particles; while gypsum, quartz, and calcite are found in bottom ash.