The change of composition during the thermal treatment of Zn(OAc)2·2H2O was analyzed by TG, FTIR and XRD characterization. At the thermal treatment temperature of 100 ℃ within 8 h, only dehydration process of Zn(OAc)2·2H2O occurred. After the thermal treatment at 120 ℃ for 4 h, Zn4O(OAc)6 was formed and its amount increased as the time of thermal treatment extended. ZnO was formed after the thermal treatment at 160 ℃ for 6 h, and most of the products were ZnO after 12 h. The products of Zn(OAc)2·2H2O under different thermal treatment conditions were used for the synthesis of 2,4-toluene dicarbamate (2,4-TDC).At the reaction temperature of 160 ℃, the yield of 2,4-TDC catalyzed by Zn(OAc)2·2H2O under the heat treatment at 100 ℃ for 8 h reached 88.1%, indicating that the catalytic activity of Zn(OAc)2 was higher at 160 ℃. When the reaction temperature reached 180 ℃, the yield of 2,4-TDC catalyzed by Zn(OAc)2·2H2O under the heat treatment at 140 ℃ for 8 h was 92.8%, showing that Zn4O(OAc)6 had a higher catalytic activity at 180 ℃.