Major anthropogenic emissions of elemental mercury (Hg0) occur from coal-fired power plants, and the emissions can be controlled successfully using NH3-SCR (selective catalytic reduction) systems with catalysts. Although the catalysts can easily convert the gaseous mercury into Hg2+ species, the reactions are greatly dependent on the flue gas constituents and SCR conditions. Numerous deNOxing catalysts have been proposed for considerable reduction in power plant mercury emissions; however, there are few studies to date of elemental mercury oxidation using SCR processes with MW- and full-scale coal-fired boilers. In these flue gas streams, the chemistry of the mercury oxidation is very complicated. Coal types, deNOxing catalytic systems, and operating conditions are critical in determining the extent of the oxidation. Of these parameters, halogen element levels in coals may become a key vehicle for obtaining better Hg0 oxidation efficiency. Such halogens are Cl, Br, and F and the former one is predominant in coals. The chlorine exists in the form of salts and is transformed to gaseous HCl with a trace amount of Cl2 during the course of coal combustion. The HCl acts as a very powerful promoter for high catalytic Hg0 oxidation; however, this can be strongly dependent on the type of coal because of a wide variation in the chlorine contents of coal.