To improve the catalytic effect of nano metal oxides on the thermal decomposition of AP， butterfly wing-shaped titanium dioxide （BW-TiO₂） has been prepared by impregnation-calcination method based on the template of a natural Morpho Butterfly wing. Field emission scanning electron microscope（FESEM）， transmission electron microscope（TEM）， X-ray diffraction （XRD）， and X-ray photoelectron spectroscopy （XPS） were used to characterize its morphology， structure， and composition. The catalytic performance of BW-TiO₂ for the thermal decomposition of ammonium perchlorate（AP） was studied using the differential scanning calorimetry（DSC）. The results show that the as-prepared BW-TiO₂ owns a anatase phase with a size of 8~12 nm， accompanying with small amount of amorphous carbon and Ti. BW-TiO₂ tightly resembles into a parallel grid skeleton structure， containing well-connected nano tubular channels and a large number of micro-pores. BW-TiO₂ illustractes excellent catalytic activity for AP thermal decomposition. Adding 5% BW-TiO₂ can reduce the high-temperature decomposition peak temperature from 429.1 to 374.1 ℃， increase the exothermic heat from 255 to 1323 J∙g^-1， and decrease the active energy from 190 to 130.9 kJ∙mol^-1.