Three-dimensional ordered thin films based on 12-phosphotungstic acid (PW(12)O(40)/SiO(2)) and lanthanide-substituted phosphotungstate (Eu(PW(11)O(39))(2)/SiO(2), Gd(PW(11)O(39))(2)/SiO(2) and Eu(P(2)W(17)O(61))(2)/SiO(2)) were constructed by an inverse opal method. using polystyrene colloidal crystal as a template. The samples were characterized by elemental analysis, XRD, IR spectra, UV-vis diffuse reflectance spectra (DR-UV-Vis) and SEM techniques. These thin films show well-defined lamellar array with inverse opal structure, and lanthanide polyoxometalate thin films exhibit photoluminescent properties. (C) 2009 Elsevier B.V. All rights reserved.