The Ag/Titania adsorbent for selective removal of the desulfurization-refractive polycyclic aromatic sulfur heterocycles (PASHs) from liquid hydrocarbon fuels was prepared, its total and the Ag specific surface area were determined and the surface reaction sites in the sorbent that may be active in the adsorptive selective desulfurization were characterized by several spectroscopic and surface science techniques. The sorbent contains Ag, Ti, O and spurious C on its surface, as by the XPS measurements. Silver is present as an oxide, as judged by the XPS Auger parameter (AP). The complementary electron spin resonance (ESR) spectroscopy confirms that the majority of Ag is present in the diamagnetic Ag1+ form, with the minor concentration (similar to 0.1% of total Ag) present as Ag2+. The findings by XPS and ESR are confirmed by the XRD, UV-vis spectroscopy and thermodynamic considerations. The supported Ag is highly dispersed on the surface of the titania support, with the particle size of similar to 30-60 angstrom depending on Ag content, with an Ag specific surface area of similar to 7-14 m(2)/g, vs. the total surface area of similar to 114-58 m(2)/g. (C) 2010 Elsevier B.V. All rights reserved.