A series of vanadia catalysts supported on the mesoporous silica SBA-15 are synthesized using an automated laboratory reactor. The catalysts contain from 0.6 up to 13.6V atoms/nm 2 and are structurally characterized by various techniques (BET, XRD, SEM, TEM, Raman, IR, UV/Vis).Samples containing up to 3.1V/nm 2 are structurally rather similar. They all contain a mixture of tetrahedral (VOx)n species, both monomeric and oligomeric. The ratio of monomeric and oligomeric species depends on the vanadia loading. At the highest loading of 13.6V/nm 2 , in addition to tetrahedral (VOx)n, also substantial amounts of three-dimensional, bulk-like V2O5 are present in the catalyst. The structural similarity of the lowloaded catalysts is reflected in their alike catalytical activity during the oxidative dehydrogenation (ODH) of propane between 380 and 480 °C. Propene, CO, and CO2 are formed as reaction products, while neither the formation of ethene nor acrolein or acrylic acid is observed in other than trace amounts. The activation energy for ODH of propane is 140 kJ/mol. The catalyst with the highest loading yields varying activation energies for different reaction conditions, which is probably related to rearrangements between bulk-like and dispersed, two-dimensional (VOx)n. Rather than the monomer to oligomer ratio, the ratio of two-dimensional to three-dimensional vanadia seems to be crucial for the catalytic properties of silica supported vanadia in the ODH of propane.