A series of novel energetic salts of 2,4,6-trinitropyridin-3-ol have been prepared and confirmed structurally. These compounds can be prepared by means of a facile synthetic procedure and show outstanding properties (detonation velocity, detonation pressure, sensitivity toward mechanical stimuli, and temperature of decomposition). They were isolated and characterized by means of elemental analysis, multinuclear (H-1, C-13) NMR spectroscopy. The structures in the crystalline state were determined by single-crystal X-ray diffraction at 296 K. From the calculated standard molar enthalpy of formation (CBS-4 M) and the densities, the Chapman-Jouguet detonation properties were predicted by using the EXPLO5 V6.02 thermochemical computer code. Their sensitivities towards impact and friction were also determined.