Abstract: Fluorine is a trace element in the coal and may cause environmental and human healthy problems during coal combustion. While coal-fired power plant is one of man-made sources of fluorine emissions in China, fluorine emission behaviors from coal-fired power plants have not been comprehensively investigated until now. A full-scale field study of fluorine emissions was conducted at six pulverized coal-fired boiler (PC) units of four coal-fired power plants in China. Flue gases were sampled from the inlets and outlets of the existing air pollutant control devices (APCDs) to investigate their effects on speciation and distribution of fluorine in the flue gas. Concurrent with flue gas, coal, bottom ash, fly ash and samples from the FGD process (desulfurization gypsum and waster water) were collected. Over 96.63% of fluorine contained in coal were released during the combustion process in the examined PC boilers, and fluorine compounds in flue gas were mainly in the form of HF. Wet FGD and dedusting devices were able to remove fluorine compounds in flue gas, wet FGD being more effective. Particulate bound fluorine in flue gas can be removed by dedusting devices. The removal efficiency of dedusting devices varied from 19.50% to 36.59% for fluorine compounds in flue gas. Bag-house filters were effective than electrostatic precipitators (ESP). Most of HF in flue gas can be removed by wet FGD devices and the average removal efficiency of wet FGD devices was 94.19%. The fluorine released from coal combustion was transferred into slag, fly ash, desulfurization gypsum and the waste water after passing through the devices for air pollution control. Fluorine in slag ranged from 0.83% to 3.37%, and approximately about 13.45%-33.80% of fluorine were contained in fly ash. A proportion of 59.60%-79.66% of fluorine came into the gypsum while the waste water was kept 1.20%-2.00% of the total fluorine. Only 2.04%-5.00% of fluorine were directly emitted into the atmosphere.