The invention discloses a purifying method of 1, 1, 1, 2-tetrafluoroethane, which comprises the steps of: contacting a 1-chlorine-2, 2-difluoroethylene-containing 1, 1, 1, 2-tetrafluoroethane crude product with a cation-modified molecular sieve under the condition of gas phase; absorbing 1-chlorine-2, 2-difluoroethylene in the 1, 1, 1, 2-tetrafluoroethane crude product by taking the cation-modified molecular sieve as adsorbent; and controlling the absorption temperature at 150-350 DEG C to obtain the purified 1, 1, 1, 2-tetrafluoroethane, wherein the cation is selected from one or several combination of the following components: H+, alkaline earth metal ion, rare-earth metal ion or transition metal ion. With chemisorption, the purifying method selectively removes HCFC-1122 in HFC-134a, has higher absorption velocity, obviously improves the adsorption capacity of the HCFC-1122, and is environment-friendly.