A new-type composite photocatalyst of three-dimensional ordered macroporous (3DOM) TiO2/C was prepared and tested in this paper. 3DOM carbon materials were first prepared by colloidal crystal templating process, and then the sols of TiO2 from tetrabutyl titanate were infiltrated in the macroporous structures via capillary force. After calcinations at nitrogen flow, TiO2/C composite materials were prepared. The obtained samples were analyzed by SEM, TEM, XRD and BET. The results indicated that macroporous TiO2/C can remain the three-dimensional ordered structure and TiO2 nanoparticles distributed in the interior of macropores uniformly. Eventually, 3DOM TiO2/C materials were used as a new-type photocatalysts to decompose the methyl orange solution under ultraviolet light, which displayed excellent catalytic activity and regenerative ability. (C) 2010 Elsevier Ltd. All rights reserved.