The sodium hydroxide calcination-hydrothermal treatment was used to modify the fly ash in this paper. The mount of alkali, the ratio of solid and liquid and the temperature of calcination were respectively studied in the process of modification. The best modified condition is that the ratio of sodium hydroxide and fly ash was 0.4:1, the ratio of solid and liquid was 1:1, and the temperature of calcination was 400°C. The zeolite-like structure was generated after modification. The modified fly ash in this paper was cheap and effective, providing a theoretical basis for wastewater treatment.