Catalytic properties of supported vanadium oxide catalysts are highly dependent on surface vanadia configuration and the nature of the support. In this study, the effects of using the same supports (silica and magnesia) from two different preparation procedures on the catalytic properties in methanol partial oxidation and on the vanadium surface structures were investigated. Both types of catalysts were prepared by the incipient-wetness method and characterized using BET, Raman spectroscopy, UV-Vis and H-2-TPR to determine the structures of vanadium on the supports' surface. Both aerogel-prepared V/SiO2 and V/MgO catalysts were more active than conventionally prepared samples in methanol partial oxidation. These differences in catalytic results are attributed to the configurations of active phase. It was also found that small vanadium phases were more active in methanol partial oxidation than larger phases.