Developing efficient ammonium perchlorate (AP) thermal decomposition catalytic nanomaterials is necessary and challenging. To achieve this goal, three-dimensional ordered macroporous (3DOM) spinel structure CoFe 2 O 4 (3DOM CoFe 2 O 4 ) were prepared by using a simple impregnation method. The prepared 3DOM COFe 2 O 4 has ordered and interconnected macroporous channels, which provide a large number of catalytic active site. After the addition of 2 wt% 3DOM CoFe 2 O 4 catalyst, the THTD value of AP decomposition was reduced by 101.81 ℃, and the decomposition activation energy was reduced from 178.42 kJ mol -1 to 134.21kJ mol -1 . It can be foreseen that 3DOM CoFe 2 O 4 is a very attractive AP thermal decomposition catalyst, which may open up new perspectives for the application of iron based materials as AP based solid propellant catalysts.