The industrial waste cenospheres of fly ash (CFA) were calcined to prepare easily recoverable adsorbent materials. Using trichloroethylene (TCE) as the target pollutant, the feasibility of adsorption and the effects of different modification parameters on the removal of pollutant were investigated. Box-Behnken design (BBD) based on response surface methodology (RSM) was applied to demonstrate the effect of the interaction of calcination temperature, calcination time and particle size on the adsorption of TCE. X-ray diffraction (XRD), Scanning electron microscope and energy dispersive spectrometer (SEM-EDS), Brunner-Emmet-Teller (BET) were employed to explore the adsorption properties of materials. The results show that the surface of CFA after calcination modification is loose and porous, resulting in the increase of specific surface area by about 2.4 times. The order of factors affecting the adsorption of TCE by modified CFA is as follows: calcination time > calcination temperature > particle size. The optimum conditions are confirmed as follows: the particle size is 0.25~0.38 mm, the calcination temperature is 640 ℃ and the calcination time is 80 min. The adsorption value of CFA is 1 344 μg/g under the optimum conditions, with the difference of 1.4% compared with the predicted adsorption of 1 326 μg/g. CFA modified by high temperature calcination have better adsorption properties, which is a kind of environmental protection material that can be easy for mass production, waste utilization and recycled.