A new and facile route has been demonstrated to improve the stability of metal oxide hollow spheres by reforming the carbon/metal-sulfide core/shell template. Unlike the traditional template methods, we first prepared a layer of metal-sulfide continuous phase on the surface of carbon spheres with a microwave irradiation technique, and then performed the calcinations to obtain desired metal-oxide hollow spheres. The significant advantage of this method is that the hollow spheres so obtained exhibit superior resistance to distortion, collapse, and shrinkage.