The selective oxidation of propene on the vanadyl and bridging oxygen sites of the fully oxidized (001) V2O5 surface and of an epitaxial vanadia monolayer supported on (001) TiO2 anatase is analyzed using periodic density functional theory (DFT). The formation of several oxygenated products, that is, allyl alcohol, propene oxide, acrolein, formaldehyde and acetaldehyde, is investigated. Selective oxidation proceeds via a Mars-van Krevelen redox mechanism and its elementary steps on the vanadia surface are identified. Propene activation occurs preferentially on the vanadyl oxygen sites, with allyl C-H and C=C bond activation being equally favorable. Supporting a vanadia monolayer on titania strongly enhances both bond activations as compared to unsupported V2O5, yielding a lower activation energy. No dominant pathway is found on V2O5, with allyl alcohol, propene oxide, and acrolein formation being almost equally favorable, while acrolein formation is expected on V2O5/TiO2. However, propene oxidation to acrolein is overall less preferable on V2O5/TiO2 than V2O5, due to the reduced activity of the supported catalyst in oxygenation reactions. The latter is linked to the creation of V3+ sites during propene oxidation over V2O5/TiO2. On the other hand, the electrons injected in the empty V 3d states during propene oxidation over V2O5 lead to the creation of V4+ sites. (C) 2012 Elsevier Inc. All rights reserved.