Distributions of mercury speciation of Hg0, Hg2+ and HgP in flue gas and fly ash were sampled by using the Ontario Hydro Method in a 220MW pulverized coal-fired boiler power plant in China. The mercury speciation was varied greatly when flue gas going through the electrostatic precipitator (ESP). The mercury adsorbed on fly ashes was found strongly dependent on unburnt carbon content in fly ash and slightly on the particle sizes, which implies that the physical and chemical features of some elemental substances enriched to fly ash surface also have a non-ignored effect on the mercury adsorption. The concentration of chlorine in coal, oxygen and NOx in flue gas has a positive correlation with the formation of the oxidized mercury, but the sulfur in coal has a positive influence on the formation of elemental mercury.