In this paper, a new-type composite photocatalyst of titania/carbon (TiO2/C) with three-dimensional ordered macroporous (3DOM) structure was successfully prepared by combining the macroporous structure of 3DOM carbon and the catalytic properties of TiO2. Under ultraviolet light, the obtained 3DOM TiO2/C materials were used to degrade Methyl Orange solution as simulated organic waste-water and had a high catalytic activity. Furthermore, compared with commercial Degussa p25 catalyst, obtained 3DOM TiO2/C materials displayed an excellent regenerative ability.