The invention discloses a method for synthesizing 4A molecular sieve by adopting the fly ash in alkaline dissolving method; the fly ash with Al2O3 being more than or equal to 36 percent (36 percent to 46 percent), and the mol ratio of the SiO2/Al2O3 being 1.8 to 2.1 is used to be mixed with alkali according to the mol ratio of Na2O/Al2O3 is 3 to 10, and to be milled and well distributed; the mixed material with the height of each layer being 4 to 8 cm is arranged inside a high-temperature furnace at the temperature of 550 to 800 DEG C to be calcined and activated for 1 to 3 hours. After being dissolved by the water, the mol ratio of H2O/Na2O is controlled to be 30 to 60, and is mixed at the temperature of 50 to 80 DEG C for 1 to 3 hours, and is colloidized, and then is heated to the temperature of 100 plus or minus 10 DEG C to be held quietly for the crystallization for 4 to 6 hours; after the reaction, the material is filtered, and is washed until the pH value is equal to 9 to 11, and is dried to get the 4A molecular sieve. The molecular sieve is white, the calcium exchanging quantity is more than or equal to 310 mg of CaCo3/g; and the sieving rate is more than or equal to 90 percent. The invention can integrally use the fly ash of the waste pollutant, and has the advantages of high utilization rate, simple process flow procedures, environmental protection, and the like.