With polymethyl methacrylate (PMMA) prepared by dispersion polymerization as sacrifice template, CeO2/PMMA composite microspheres were prepared by inorganic precursor homogeneous precipitation and self-assembly. The CeO2 hollow nanospheres were obtained after the polymer sphere template was removed through calcination at a suitable temperature. Scanning electron microscope, transmission electron microscope, fourier transform infrared spectroscopy, X-ray photoelectron spectrum, X-ray diffraction and thermogravimetry were employed to characterize the structure and morphology of the CeO2 hollow nanospheres. The results reveal that the face-centered cubic-phase CeO2 hollow nanospheres with a diameter of about 0.9 μm as well as the thin shell thickness about 40 nm are prepared. It indicates that adding CeO2 hollow nanospheres in butyl rubber as packing materials can obviously improve its low frequency damping capacity in different frequency (0~180 Hz).