The Kozani-Ptolemais-Amyntaio basin constitutes the principal coal field of Greece. Approximately 50% of the total power production of Greece is generated by five power stations operating in the area. Lignite samples, together with the corresponding fly ash and bottom ash were collected, over a period of 3 months, from the power plant of Amyntaio and analyzed for their content in 16 trace elements. The results indicate that Y, Nb, U, Rb, Zr, Ni, Pb, Ba, Zn, Sr, Cu, and Th demonstrate an organic affinity during the combustion of lignite, while V has an inorganic affinity. Three elements (Co, Cr, and Sc) show an intermediate affinity.