MgO-supported vanadium oxide catalysts with different vanadium loadings have been prepared by wet impregnation and grafting using ammonium metavanadate or VOCl3 as precursor, respectively. The prepared catalysts have been characterized by several techniques Such as XRD, FT-IR, DR-spectroscopy, BET, V-51 solid-state NMR, SEM and EDX. For comparison, three different phases of magnesium vanadate (meta-beta-MgV2O6, pyro-alpha-Mg2V2O7, and ortho-Mg3V2O8) have been synthesized as reference materials for the Structural characterization. The catalytic activity of the prepared catalysts was evaluated for the liquid-phase oxidation of cyclohexane as a model reaction to obtain cyclohexylhydroperoxide, cyclohexanol and cyclohexanone with PCA as co-catalyst. The results show that VOx/MgO catalysts containing isolated VO4 species either impregnated or grafted do not show considerable activity in the oxidation process. In contrary, catalysts with higher vanadium loading, which contain ortho-Mg3V2O8, pyro-Mg2V2O7 and V2O5 phases as Surface Species show conversions Lip to 70% and TONS LIP to 34,700. Compared to previously Studied support materials for this catalytic system the leaching behavior is significantly improved. (C) 2009 Elsevier B.V. All rights reserved