The lattice-work structure of a rutile TiO2(001) surface, which is faceted to {114} plane, was studied by combining scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption. ne structure (NEXAFS) and density functional theory (DFT) calculations. Synchrotron XPS and NEXAFS spectra taken for the faceted surface indicated that this surface possesses a stoichiometric composition. We propose a new stoichiometric structure model on the basis of XPS, NEXAFS, and atomically-resolved STM observations. DFT calculations revealed that the present stoichiometric model is energetically more favorable compared to the previously proposed models. (c) 2008 Elsevier B.V. All rights reserved.