A composite material of ZIF-67 and hydroxylated carbon nanotube (CNTOH) was prepared by a simple method and applied to catalytic decomposition of ammonium perchlorate (AP). The AP-based composites with ZIF@CNTOH added were tested by thermal analysis methods including differential scanning calorimetry (DSC) and thermogravimetric (TG). The results showed that the low temperature decomposition peak of the samples was weakened and even disappeared after the addition of the catalyst, and the high temperature decomposition peak was significantly advanced. When the content of CNTOH in ZIF@CNTOH is 5% and ZIF@CNTOH accounts for 5% in AP composite, the pyrolysis peak temperature was reduced from the original 409.7 degrees C to 298.8 degrees C, proved the significantly catalytic effect. This is mainly due to the effective uniform loading of transition metal ions on ZIF and the excellent electrical and thermal conductivity of CNTOH. The combination of them makes it achieve the best synergistic catalytic effect.