Abstract Three fully optimized geometries of 3-nitro-1,2,4-triazol-5-one–hydrogen fluoride (NTO–HF) complexes have been obtained with density functional theory (DFT) method at the B3LYP/6–311++G** level. The intermolecular interaction energy is calculated with zero point energy (ZPE) correction and basis set superposition error (BSSE) correction. The greatest corrected intermolecular interaction of the NTO–HF complexes is −34.155 kJ/mol. Electrons in complex systems transfer from NTO to HF. Natural bond orbital (NBO) analysis is performed to reveal the origin of the interaction. The strong hydrogen bonds contribute to the interaction energies dominantly. Frequency calculations are carried out on each optimized structure, and their IR spectra are discussed. Vibrational analysis show that there are large red-shifts for H–X (X = N and F) stretching vibrational frequencies in the NTO and hydrogen fluoride complexes. The changes of thermodynamic properties from the monomer to complexes with the temperature ranging from 200 K to 1500 K have been obtained using the statistical thermodynamic method. It is found that two of three NTO–HF complexes can be produced spontaneously from NTO and HF at room temperature.