An energetic binder epoxy poly glycidyl nitrate (e-PGN) with a molecular weight of about 1244 gr/mol was synthesised via end modified poly glycidyl nitrate (PGN) is presented in the paper. This structure was characterised by the number of epoxy groups, infrared spectroscopy, and nuclear magnetic resonance. The thermal degradation behavior of e-PGN was studied by thermo gravimetric analysis (TG) and differential scanning calorimetry (DSC) under nitrogen atmosphere at different heating rates. The glass transition temperature (Tg) was measured to determine the compatibility of energetic plasticizer with the binder in the mixture of plasticizer/binder and compared with the results of e-PGN, and initial decomposition temperature in e-PGN was studied using the DSC method. The DSC results showed that the glass transition temperature of a mixture of 20 % Bu-NENA/e-PGN mixture (Tg = −56 °C) was lower than e-PGN (Tg = −37.78 °C) that shows the most compatible plasticizer is Bu-NENA. The activation energy of degradation e-PGN and e-PGN-20% Bu-NENA were calculated with DSC by the model-free methods and compared with the results of AKTS software in version 3.51(2013-07-10). The activation energy of exothermic decomposition of the e-PGN and e-PGN-20% Bu-NENA were calculated by the Kissinger, Flynn–Wall–Ozawa, Starink, and AAdvanced kinetics and technology solutions (Friedman) methods. Finally, the half-life prediction of the e-PGN and e-PGN-20% Bu-NENA were investigated.