In order to study the effect of additives on mercury speciation in coal-fired derived flue gases, the additives experiment was conducted in one 110MW coal-fired power plant, the additives including calcium bromide and iron oxide. Taking advantage of the Ontario Water Act (OHM) and sorbent tube method, mercury at the denitration (SCR) entrance and export and desulfurization (WFGD) entrance was sampled and the variation of mercury before and during adding the additives was analyzed. The results show that the additives of calcium bromide can oxidize elemental mercury and contribute to increasing the proportion of divalent mercury, and in denitration device, the ratio of divalent mercury in flue gas shows an increasing trend along with the increasing of calcium bromide. However, there is no such trend appearing at desulfurization entrance. In addition, the additives of iron oxide have no obvious effect on the oxidation of elemental mercury in flue gas. Adding a small amount of iron oxide has little effect on the form of mercury, and may even reduce the proportion of divalent mercury. VC 2016 American Institute of Chemical Engineers Environ Prog, 35: 1566-1574, 2016