<p>In order to study the thermal hazard of butyl nitrooxyethyl nitramine (BuNENA), differential scanning calorimetry (DSC) was used to measure the thermal decomposition curves at heating rates of 2.5 °C·min⁻¹, 5&#xa0;°C·min⁻¹, 10&#xa0;°C·min⁻¹ and 20&#xa0;°C·min⁻¹. A thermal decomposition kinetic model was established by fitting DSC curves and the thermal hazards of BuNENA was assessed, which can effectively support the intrinsic safety design of BuNENA production and transportation processes, the establishment of scientific early warning systems, and the formulation of safety precautionary measures. The result indicates that BuNENA begins to thermal decomposition at 158.2–195.7&#xa0;°C. As the heating rates increase, both the initial decomposition temperature (<i>T</i>₀) and the peak temperature (<i>T</i>_p) moved toward the high temperature. The Freidman method indicate that the thermal decomposition of BuNENA is a complex process, the activation energy (<i>E</i>_a) and pre-exponential (ln <i>A</i>) are 90–190&#xa0;kJ·mol⁻¹ and 17–37&#xa0;s⁻¹, respectively. The kinetic model has been established comprising continuous reactions which contain three steps, and kinetic parameters of each step are obtained. Additionally, the curve of time to maximum (<i>TMR</i>_ad) illustrate the process temperature should not be higher than 95.17&#xa0;°C during the preparation and use of BuNENA, and the ambient temperature should be maintained below 74&#xa0;°C during transportation.</p>