A new layered compound K2.33Sr0.67Nb5O14.335 was prepared and its full structure was characterized by single crystal diffraction of K2.33Sr0.67Nb5O14.335, which belongs to Tetragonal layered perovskite phase. The band structure of K2.33Sr0.67Nb5O14.335 was calculated by CASTEP code based on the density functional theory (DFT). H2.33Sr0.67Nb5O14.335 was prepared by a proton exchange of K2.33Sr0.67Nb5O14.335, and followed with successive reaction to obtain Pt incoporated sample. Using H2.33Sr0.67Nb5O14.335/Pt as catalyst, the photocatalytic H-2 evolution rate reached 153.1 cm(3) h(-1) g(-1) in 10 vol.% methanol aqueous solution under irradiation with wavelength more than 290 nm from a 100 W mercury lamp. (C) 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.