The two kinds of energetic ionic salts IMI·TNR and 4-AT·TNR (IMI=imidazolium, 4-AT=4-amino-1, 2, 4-triazolium, TNR=2, 4, 6-trinitro resorcinol) were synthesized. The crystal structures were determined by IR, elemental analysis and X-ray single crystal diffraction. The thermal decomposition mechanisms were investigated with DSC and TG. The non-isothermal reaction kinetic parameters were researched by Kissinger′s method and Ozawa′s method on the basic of DSC results. The mpact sensitivity, friction sensitivity and flame sensitivity for two ionic salts was measured. Results show that the crystal of IMI·TNR is monoclinic, space group P2₁/c with a density of 1.779 g·cm^-3 and decomposition temperature of 223.4 ℃ and 4-AT·TNR is triclinic, space group P-1 with a density of 1.772 g·cm^-3 and decomposition temperature of 259.8 ℃. The values of T_b, ΔS^≠, ΔH^≠ and ΔG^≠ are 222.4 ℃, -213.06 J·K^-1·mol^-1, 302.89 kJ·mol^-1and 407.10 kJ·mol^-1 for IMI·TNR and 257.3 ℃, -221.31 J·K^-1·mol^-1, 129.66 kJ·mol^-1 and 243.24 kJ·mol^-1, respectively. They are insensitive to impact, friction and flame stimuli.