Hierarchical Cu2O nanostructures have been successfully fabricated on a large scale using copper acetate and glucose as starting reactants, CTAB as an additive via a microwave-assisted process. The influences of CTAB dosage and reaction time on the morphology of the products were investigated. The resulting Cu2O nanostructures were characterized by means of X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). FESEM images show that the Cu2O nanostructures are microsphere, which are composed of nanoparticles. The concentration of CTAB plays a key role in the growth of Cu2O nanostructures under experimental conditions. The possible formation mechanism of these hierarchical Cu2O nanostructures has been proposed. Meanwhile, the catalytic performances of these Cu2O microspheres for thermal decomposition of ammonium perchlorate (AP) were investigated using DSC. The results revealed that Cu2O have a great influence on the thermal decomposition of AP. The additions of Cu2O powders lower the high decomposition temperature of AP.