In this study, CeO2 hollow spheres were synthesized via a facile surfactant-assisted solvothermal route. The synthesized products were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, and N-2 adsorption-desorption. Different solvent species has been demonstrated as the key factor responsible for the controlled morphologies. Furthermore, both the water and the oleic acid were crucial to the formation of CeO2 hollow spheres. The possible formation mechanism of CeO2 hollow spheres has been preliminary discussed.