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3-nitro-1,2,4-triazol-5-one (NTO) is the main component of insensitive munitions (IM) formulation because of its outstanding insensitive properties. In this paper, a series of NTO/HMX-based composite explosives were prepared and characterized. The study focuses on the effect of NTO on the performance of the formulations, especially the safety performance. The results revealed that the mechanical sensitivity of formulations was associated with NTO content, as well as the thermal conductivity, specific heat capacity and Arrhenius parameters. Then, the high amount of NTO using in formulation was proved to be helpful for NTO/HMX-based formulation to exhibit good thermal safety. Besides, by accelerating rate calorimeter (ARC) and a modified cook-off equipment, the pressure and pressure rise rate were proved as the important indicator for judging the thermal safety performance in confined spaces. Finally, the numerical simulation was used as a credible method for predicting the respond temperature of cook-off experiment.