An energetic salt, sodium nitroformate(NaNF), was synthesized and characterized by elemental analysis, IR and UV spectra, and its crystal structure was fi rst determined by single crystal X-ray diffraction. The structure exhibits two types of π–π stacking interactions between the nitroformate anions, i e, the parallel-displaced and T-shaped confi gurations. Furthermore, the thermal decomposition mechanism was investigated by DSC, TG-DTG and FTIR techniques. The kinetic parameters of the thermal decomposition were also calculated by using Kissinger’s and Ozawa–Doyle’s methods. The results show that NaNF has a good thermal stability, which is attributed to the π–π stacking interactions. An energetic salt, sodium nitroformate (NaNF), was synthesized and characterized by elemental analysis, IR and UV spectra, and its crystal structure was fi rst determined by single crystal X-ray diffraction. The structure exhibits two types of π-π stacking interactions between the nitroformate anions, ie, the parallel-displaced and T-shaped confi gurations. ie, the thermal decomposition mechanism was investigated by DSC, TG-DTG and FTIR techniques. The kinetic parameters of the thermal decomposition were also calculated by using Kissinger’s and Ozawa-Doyle’s methods. The results show that NaNF has a good thermal stability, which is attributed to the π-π stacking interactions.