Cerium-doped titania inverted opals with powder and film morphologies were synthesized from cerous nitrate and tetrabutyl titanate in the interstitial spaces of a polystyrene opal. This procedure involves infiltration of precursors into the interstices of the polystyrene opal template followed by hydrolytic polycondensation of the precursors to amorphous titania and removal of the polystyrene opal by calcination. The morphologies of opal and inverse opal were characterized by scanning electron microscope (SEM). Powder X-ray diffraction (XRD) allows one to observe the influence of doping degree on the grain size. And the XPS investigation showed the doping structure of cerium. The synthesis of cerium-doped titania inverted opals provides an opportunity to electrically and optically engineer the photonic band structure and the possibility of developing tunable three-dimensional photonic crystal devices. (C) 2007 Elsevier B.V. All rights reserved.