Coal as well as fuel oil combustion generates emissions of potentially toxic trace pollutants including organic and inorganic chemical compounds besides major pollutants. A study on As, Cd, Co, Cr, Cu, Hg, Fe, Mn, Ni, Pb, Se, and Zn emissions from a 220 MW coal-fired power plant equipped with a electrostatic precipitators (ESPs) and 6 MW oil fired-power plant was carried out, using stack monitoring kit, Envirotech APM 620, which is similar to EPA Method 29. Simultaneous sampling of coal, fuel oil, oil waste, bottom ash, fly ash, flue gases, and particles associated with the gas phase has been performed. This sampling method was used for trace metal sampling. The content of all these metals in coal, oil, oil waste, bottom ash, fly ash have been determined by XRF, whereas their contents in the flue gases, and particles associated with the gas phase has been analyzed with ICP-AES. The mass balances obtained for trace elements were satisfactory in case of fuel oil based power plant, whereas in case of coal fired power plant, the mass balance for all the trace elements were below 50% except for the As, Se, and Hg. The enrichment factors for all trace metals was <1 in both cases. The above sampling method is moderately adequate method for trace element sampling in coal as well as oil fired power plants except for Hg. The results indicate that trace metals emissions were higher in coal-based power plant than the fuel oil-fired power plant.