Coal fly ash is an industrial waste generated from the thermal power plant and a large amount of it could be produced annually in the world, which can cause serious environmental problems. Reutilization of coal fly ash could be imperative to alleviate the environmental pressure. Thus, in the present study, coal fly ash was used as silicon source for the synthesis of calcium silicate hydrates (C-S-Hs) though the desilication process. Two kinds of C-S-Hs was synthetized at 100°C and room temperature respectively, with the fixed Ca/Si molar ratio of 1.2, and adopted as the adsorbents for phosphate. The properties of them were characterized using XRD, SEM, FTIR, TG-DTA as well as surface area and pore analysis. Compared to C-S-H synthesized from high temperature, the C-S-H obtained at room temperature possessed high purity and larger surface area. Therefore, synthesis by agitation at room temperature could be an alternative method to produce C-S-H materials from desilication liquid of coal fly ash, and this could save infrastructure cost and energy consumption. Both C-S-H materials have good ability to immobilize phosphate pollutant (higher than 100 mg•g-1). The specific mechanisms of phosphate removal using C-S-H include several steps: firstly, phosphate ion was immobilized by binding with Ca 2+ and forming aggregates, and the C-S-H structures were gradually corroded. Eventually, hydroxyapatite was formed after the C-S-H structure was totally destroyed.