Fly ash samples were collected from the electrostatic precipitator (ESP) of a 600MW pulverized coal boiler firing Zhungeer bituminous coal in China to evaluate and explore its mercury adsorption capacity and mechanism. Samples characterization was conducted to feature their morphologies correlated to mercury content, and experimental studies on mercury adsorption in a fixed-bed apparatus were carried out to further verify its mercury adsorption availability. Based on the experimental data, adsorption isotherm was modeled with Langmuir, Freundlich, and Temkin equations. Adsorption kinetic analysis was also performed. The results show that mercury content of fly ash samples is associated with particle size, unburned carbon content and functional groups of Al-O/Si-O or Si-O-Si/Si-O-Al tetrahedron on fly ash. Increase of initial mercury concentration is beneficial to promote mercury adsorption due to the enhancement of mercury diffusion force onto the fly ash surface, mercury intraparticle diffusion rate and initial mercury adsorption rate. Fly ash with medium size displays better mercury adsorption capacity. Smaller particle size results in higher specific surface area, but brings about low specific surface area utilization rate for mercury adsorption. Freundlich isotherm equation presents better fitting result, indicating that fly ash surface is non-uniform. Mercury adsorption on fly ash at 120 oC is mainly physisorption enhanced by chemisorption with ΔG at .36.73 kJ/mol. The pseudo-first-order kinetic model can describe the adsorption process more accurately and predict mercury adsorption capacity of fly ash preferably, showing that mercury adsorption on fly ash surface in fixed-bed is controlled dominantly by external mass transfer.