Cu2(bdc)2 (bpy) metal-organic framework (MOF) was prepared by solvothermal method and the structure was characterized by powder X-ray diffraction (PXRD), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR). The specific surface area and the pore size distributions was estimated by Brunauer–Emmett–Teller (BET) method and micropore (MP) plot. This metal-organic framework was used as catalyst to improve the thermal decomposition of ammonium perchlorate (AP) and thermal behaviors of the mixed samples containing the catalyst and ammonium perchlorate were investigated by thermogravimetric analysis (TGA) and differential scanning calorimetric (DSC) experiments. The results showed that in the catalyzed samples, the heat released from thermal decomposition of ammonium perchlorate is much higher (more than 3 times in sample containing 4% by weight of the metal-organic framework as catalyst) and thermal decomposition temperature was significantly lower than that of pure AP (about 110 °C decrease in sample containing 2% by weight of catalyst). Thermal decomposition temperature range of AP was reduced from 178 °C to 105 °C and 61 °C in the samples containing 4% and 2% by weight of catalyst respectively. The results of kinetic calculations obtained from Kissinger method showed effective catalytic performance of this metal-organic framework by increasing the thermal decomposition rate constant of AP more than 1.8 times at a much lower temperature.