The structure and reactive properties of alumina-supported molybdena, vanadia and molybdena-vanadia above monolayer coverage are studied by XPS, XRD, Raman spectroscopy and methanol temperature-programmed surface reaction (TPSR). Alumina-supported series are prepared by impregnation. Reference bulk Mo-V-Al oxide systems are prepared. The bulk Mo-V-Al oxide system provides structural references to characterize the alumina-supported series. The Raman bands of AlVMoO7 are reported here for the first time, to the best of our knowledge. It is shown that the chemistry of the bulk Al-V-Mo system is also present in the alumina-supported Mo-V oxide catalysts. Methanol TPSR data show that the systems possess essentially redox activity. (c) 2006 Elsevier B.V. All rights reserved.