Coordination compounds based on tetrazole compounds may be potential candidates for energetic materials. A solvent free compound with three dimensional network [Ni(pytza)2]n was prepared from a solvothermal reaction by using Hpytza and Ni(ClO4)2·6H2O, where Hpytza=5-(4-pyridyl)tetrazole-2-acetic acid. This compound was characterized by elemental analysis, IR and single crystal X-ray diffraction. Thermal behavior of the compound was characterized by differential scanning calorimetry (DSC) and thermogravimetric-differential thermogravimetric (TG-DTG). Furthermore, the apparent activation energy (E); Arrhenius equation; critical temperature (Tp); oxygen balance (OB %); entropy of activation (△S), enthalpy of activation (△H), and free energy of activation (△G) of the decomposition process were discussed, as well. This compound has a potential as energetic material.