The oxidative dehydrogenation of propane (ODP) on the anatase supported vanadia catalysts (VOx/TiO2) have been investigated using periodic DFT calculations. Free energy profiles indicate that the first C-H activation step is the rate-determining (RD) step and the transition state (TS) of the propene formation step is the RD-TS. ODP activity can be tuned by vanadia dispersion and support surface via the modification of the electronic structure of the active oxygen sites. For the RD step, on both dimer VOx/TiO2 catalysts terminal sites have higher activity. On monomer VOx/TiO2 (1 0 0) terminal and interface sites exhibit similar activity, while on monomer VOx/TiO2 (0 0 1) interface sites have higher activity. With increasing vanadia loading, the formation of propene changes from propyl radical mechanism to a concerted propoxide one. The results suggest that TiO2 (1 0 0) is a better support surface. Terminal and interface oxygen sites act cooperatively as the first and second C-H bond activation centers, respectively. (C) 2013 Elsevier B.V. All rights reserved.