The properties of fly ash in coal-fired boilers influence the emission of mercury from power plants into the environment. In this study, seven different bitumous coals were burned in a full-scale 100 MWe pulverized coal combustion boiler and the derived fly ash samples were collected from a mechanical hopper (MH) and an electrostatic precipitator hopper (ESP). The mercury content, specific surface area (SSA), unburned carbon, and elemental composition of the fly ash samples were analyzed to evaluate the correlation between the concentration of particulate-bound mercury and the properties of coal and fly ash. For a given coal, it was found that the mercury content in the fly ash collected from the ESP was greater than in the fly ash samples collected from the MHP. This phenomenon may be due to a lower temperature of flue gas at the ESP (similar to 135 degrees C) compared to the temperature at the air preheater (similar to 350 degrees C). Also, a significantly lower SSA observed in MH ash might also contribute to the observation. A comparison of the fly ash samples generated from seven different coals using statistical methods indicates that the mercury adsorbed on ESP fly ashes has a highly positive correlation with the unburned carbon content, manganese content, and SSA of the fly ash. Sulfur content in coal showed a significant negative correlation with the Hg adsorption. Manganese in fly ash is believed to participate in oxidizing volatile elemental mercury (Hg-0) to ionic mercury (Hg2+). The oxidized mercury in flue gas can form a complex with the fly ash and then get removed before the flue gas leaves the stack of the boiler.