Carbon-modified TiO2 photocatalysts with a hierarchical meso-/macroporous structure were prepared through direct hydrolyzation of n-tetrabutyl titanate in the dodecylamine solution and subsequent calcination under nitrogen atmosphere. The resulting photocatalysts were characterized by X-ray diffraction, scanning and transmission electron microscopy, nitrogen sorption analysis, X-ray photoelectron spectroscopy, and UV-vis spectroscopy. A well-defined hierarchical macrochannel-like structure of mesoporous nanoparticle assembly with a predominant anatase phase was observed in the synthesized carbon-modified titania materials, exhibiting obviously high absorption in the wavelength range of 400-800 nm. It is revealed that carbon could not only substitute partly Ti in the form of Ti-O-C bond but also substitute 0 in the form of O-Ti-C, besides amorphous interstitial carbon atoms were synchronously introduced, benefitting the improvement of solar light photocatalytic activity. The synthesized hierarchical carbon-modified titanias materials exhibited excellent photocatalytic performance in the photodegradation of Rhodamine B dye, suggesting their promising potential as effective solar photocatalysts for organic waste degradation. (C) 2010 Elsevier B.V. All rights reserved.