High surface area (>300 m(2) g(-1)) nano-structured TiO2 oxides (ns-T) were used as CoMo hydrodesulfurization catalyst support. Cylindrical extrudates were impregnated by incipient wetness with Mo (2.8 Mo at. nm(-2)) and Co (atomic ratio Co/(Co + Mo) = 0.3). Characterization of impregnated precursors was carried out by N-2 physisorption, XRD and atomic absorption and laser-Raman spectroscopies. Sulfided catalysts (400 degrees C, H2S/H-2) were studied by X-ray photoelectronic spectroscopy. As indicated by XRD and after various preparation steps (extrusion, Mo and Co impregnation and sulfiding) the nano-structured material was well preserved. XPS analyses showed that Co and Mo dispersion over the ns-T support was much higher than that on alumina. Very high surface S concentration suggested that even ns-T was partially sulfided during catalyst activation. Dibenzothiophene hydrodesulfurization activity (5.73 MPa, 320 degrees C, n-hexadecane as solvent) of CoMo/ns-T was two-fold to that of an alumina-supported commercial CoMo catalyst. The improvement was even more remarkable in intrinsic pseudo kinetic constant basis. No important differences in selectivity over the catalysts supported on either Al2O3 or ns-T were observed, where direct desulfurization to biphenyl was favored. Both Mo dispersion and sulfidability were enhanced on the ns-T support where Mo4+ fraction was notably increased (similar to 100%) as to that found on CoMo/Al2O3. (c) 2005 Elsevier B.V. All rights reserved.