A modified sol-gel technique with the aid of a structure-directing surfactant was employed to synthesize highly crystalline mesoporous-assembled V2O5 nanosheet under mild conditions. The synthesized V2O5 nanosheet was systematically characterized by TG-DTA, XRD, N-2 adsorption-desorption, high resolution TEM, and UV-visible spectroscopy analyses. The characterization results revealed that the synthesized V2O5 nanosheet exhibited not only high crystallinity but also narrow pore size distribution in the mesoporous range. The photocatalytic H-2 production activity of the synthesized mesoporous-assembled V2O5 nanosheet from both self photoexcitation and dye photosensitization systems under visible light irradiation was also found to be higher than that of a commercially available V2O5 powder. (C) 2010 Elsevier B.V. All rights reserved.