The kinetic parameters of thermal decomposition reactions are important in predicting the potential of energetic material systems for the thermal explosion. In this study, the thermal decomposition behaviors of three polymer‐bonded explosive samples based on hexogen and nitrocellulose were evaluated and compared to the hexogen sample. The results show that the binder based on nitrocellulose has negatively affected on the thermal stability of polymer‐bonded explosives. The activation energy of the polymer‐bonded explosive was reduced by approximate 25 % compared to that of hexogen. Moreover, while hexogen exhibited an estimated shelf‐life of 70 years, the polymer‐bonded explosives could remain their safety and explosion properties for only around 45 years. Finally, increasing the nitrocellulose content from 3.75 to 6.67 wt.% reduced the thermal stability and shelf‐life of the polymer‐bonded explosive.