Rainout from wet-stack took placed in many thermal power plants with WFGD system. Research on causes of the rainout is important to solve the problem. The objective of this research is to analyze the mechanism of rainout. Field study was performed to collect experimental data in one thermal power plant, including the amount of desulfurization slurry carried by wet flue gas, liquor condensate from wet duct, and droplets from the wet stack. Source apportionment analysis was carried out based on physical and chemical data of liquid sample and solid sample. The result showed that mist eliminator operated well, which met the performance guarantee value. But the total amount of desulfurization slurry in flue gas and the sulfate concentration in liquid condensate discharge from the wet duct/stack increased. The liquid condensate accumulated in the wet duct/stack led to liquid re-entrainment. In conclusion, the rainout in this power plant was caused by the short of wet ductwork or liquid discharge system, the droplets caused by re-entrainment carried by the saturated gas released from the stack. The main undissolved components of the rainout were composite carbonate and aluminosilicate. Although ash concentration in this WFGD met the regulation criteria, source apportionment analysis showed that fly ash contributed to rainout was accounted for 60%. This percentage value was same as the data of solid particles in the condensate. It is important to optimize the wet ductwork, wet stack liner, liquid collectors and drainage. Avoiding the accumulation from saturated vapor thermal condensation is an effective way to solve the wet stack rainout.