The Zn-BTC, Co-BTC and Zn-Co-BTC series metal-organic frameworks were successfully prepared by a gas-solid two-phase flow (GSF) method with zinc nitrate, cobalt nitrate, and 1,3,5-benzenetricarboxylic acid (H3BTC) as raw materials. Single-crystal structures were obtained by the solvothermal method, and the structure and thermal stability of the target materials were characterized by FT-IR, XRD, SEM, energy-dispersive X-ray spectroscopy and DTA. The three obtained target substances were applied to catalyze the thermal decomposition of ammonium perchlorate (AP), and the performance was longitudinally compared. Testing and calculation results showed that when 10 wt% of the sample was added, monometallic Zn-BTC and Co-BTC lowered the AP pyrolysis temperature by 64.1 °C and 92.3 °C, respectively, and their activation energies decreased from 215.96 kJ mol-1 to 136.27 kJ mol-1 and 125.29 kJ mol-1, respectively. Bimetallic Zn-Co-BTC lowered the AP pyrolysis peak by 103.1 °C and the activation energy to 115.56 kJ mol-1, indicating that the series of samples exhibited good catalytic performance, and the catalytic effect of the bimetallic sample was significantly better than those of the monometallic samples.