To determine the decomposition kinetic parameters of urotropin, the differential scanning calorimeter(DSC) and accelerating rate calorimeter(ARC) were employed to study its thermal behavior at different heating rates. DSC results show that the exothermic decomposition and endothermic melting are overlapped, the activation energies of the two peaks in isothermal test are all about 150 kJ ·mol^-1. The temperature at which the time to maximum rate is 24 h(T_D24) was calculated by the AKTS code, the value was 216.26 ℃. ARC results show that the initial temperature of urotropin is 230.28 ℃, T_D24 is 212.5 ℃, which is near to the prediction (216.26 ℃)based on the isothermal DSC results.