The effect of tungsten incorporation in the surface composition and its catalytic performance is evaluated for alumina supported Mo-V-O, Mo-W-O, V-W-O and Mo-V-W-O nanostructurated-oxide catalysts. The characterization results reveal that the surface of Mo-V-W-O catalysts is further different from the binary counterparts, due to the presence of stabilized and reduced structures dispersed on the support. Such species are not present in the Mo-V-O catalysts; indicative that tungsten acts as a structural-chemical promoter. The in situ FT-IR study of these catalysts under propane + oxygen atmosphere showed that Mo-V-W-O catalyst is able to thermally activate the propane oxotransformation and ODH-products are registered in the gas-phase whereas oxygenate-compounds are detected on the surface of catalysts. (c) 2006 Elsevier B.V. All rights reserved.