Porous hollow CeO 2 microspheres were fabricated using negative-charged PS microspheres as templates by a facile method. The hollow CeO 2 microspheres were characterized by X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and N 2 adsorption-desorption. The results showed that the as-synthesized hollow CeO 2 microspheres are well monodisperse and uniform in size. The porous shells of hollow microspheres are relatively rough and composed of tiny nanoparticles. The external diameter, internal diameter, and shell thickness of hollow CeO 2 microspheres are about 190, 160, and 15 nm, respectively. A possible mechanism for the formation of hollow CeO 2 spheres was also discussed.