Ammonium nitrate（AN）, used as oxidizer of low signature and smokeless propellants, is a promising candidate. However there are some problems for AN-based propellant in ignition and combustion. One way to resolve ignition and combustion difficulties for AN-based propellant is to lower AN decomposition temperature, and to accelerate the thermal decomposition of AN. Effect of metal oxide, organic metal salt (OME), energetic binder and hexanitrohexaazaisowurtzitane(HNIW) on the thermal decomposition of AN are studied by DSC and TG-DTG. Results show that catalysts lower the endothermic decomposition temperature of AN to a certain extent and energetic components accelerate the exothermic decomposition process of AN.