The wet impregnation of ammonium heptamolybdate onto silica-alumina is used to prepare MoO3/SiO2-Al2O3 heterogeneous metathesis catalysts. The preparation is inspected in details in conjunction with physico-chemical characterization tools with the aim to identify the parameters that dictate the genesis of active and inactive metathesis species. The effects of the MoO3 loading and of the calcination temperature are systematically explored. The samples are characterized by N-2-physisorption, ICP-AES, XRD, Raman, Al-27 MAS-NMR and XPS and evaluated in the metathesis of propene to butene and ethene. Particular attention is brought to the interaction of the mesoporous silica-alumina support with the active component, to the decomposition of the precursor salt and to the location of the molybdenum oxide phase with respect to the pores of the support. It is shown that the temperature of calcination influences markedly the performances of the catalyst. High temperature treatments are necessary to decompose efficiently the Mo salt precursor. In the metathesis of propylene, the performances are levelling off when the MoO3 loading is increased above similar to 8 wt.%. This effect is correlated to the build up of MoO3 crystals and of Al-2(MoO4)(3) at relatively high loading. (C) 2010 Elsevier B. V. All rights reserved.