Two multiligand coordination compounds, [Mn(AZT)4(H2O)2](PA)2·4H2O (1) and [Co(AZT)2(H2O)4](PA)2 (2), were synthesized with 3-azido-1,2,4-triazole (AZT) as a ligand and picrate (PA) as a counteranion and characterized by elemental analysis and FTIR spectroscopy. The crystal structures were determined by single-crystal X-ray diffraction. The results show that the crystals of 1 and 2 have a triclinic space group (P) and orthorhombic space group (Pbca), respectively. Moreover, 1 and 2 have distorted octahedral structures. Their thermal decomposition mechanisms were investigated by differential scanning calorimetry and thermogravimetric analysis. The experimental data showed that the energies of combustion were approximately equal to the energies of combustion of 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and 1,3,5,7-tetranitro-1,3,5,7-tetraazocane (HMX). The nonisothermal kinetic parameters were studied by applying the methods of Kissinger and Ozawa. The sensitivity properties showed that 1 and 2 had a higher flame sensitivity than 2,4,6-trinitrotoluene, RDX, and HMX.