Three-dimensionally ordered macroporous (3DOM) CuO is prepared by colloidal crystal templated method. The obtained 3DOM structure with about 230[Formula: see text]nm pore diameter is composed of small CuO windows. The special structured CuO is used as a catalyst for thermal decomposition of ammonium perchlorate (AP) and its catalytic activity is measured by simultaneous thermogravimetry-differential scanning calorimetry (TG-DSC) techniques. Test results show that thermal decomposition performance is significantly improved after adding 2[Formula: see text]wt.% 3DOM CuO.