New model catalysts were prepared by applying DC magnetron sputter deposition of vanadia onto ZrO2/SiO2 and TiO2/ZrO2/SiO2 Supports and were characterized by X-ray diffraction (XRD), X-ray energy dispersive spectrometry (EDX), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma emission spectroscopy (ICP) and catalytic activity towards propane and isobutane oxidative dehydrogenation. Titania interlayer enhances oxidative dehydrogenation activity and decreases the total oxidation side reactions. A Mars-van Krevelen mechanism is operative. (c) 2006 Elsevier B.V. All rights reserved.