We use density functional calculations to elucidate the modulation of catalytic properties of oxide surfaces by replacement of some of the host cations with other metal dopants. In particular, we are interested in the influence of dopants on the surface properties relevant to oxidation and oxidative dehydrogenation reactions. Many oxidation reactions operate via the Mars and Van Krevelen mechanism in which the oxygen atom from the oxide surface is supplied to the reactant that is getting oxidized, leaving behind a surface oxygen vacancy. Hence, the energy needed to create an oxygen vacancy from the oxide surface can be used to calibrate the propensity of the surface towards the Mars and Van Krevelen mechanism. We have performed calculations on doped ZnO, MgO, CaO, BaO and CdO to identify the trends in the energetics of surface oxygen vacancy formation. We show that the doped oxide can generate two qualitatively different types of reactive oxygen species. In one scenario, the substituted dopant may be “activated” to adsorb an oxygen molecule, which is in turn made reactive via electron transfer from the dopant. In this instance, it also possible to generate peroxo complexes, which are crucial for the activation of hydrocarbons. In the second scenario, the dopant activates the oxide surface by facilitating the creation of a surface oxygen vacancy. The reactive oxygen species generated in the two different scenarios also leads to differences in reactivity of the oxide in oxidation reactions. We also elucidate how the oxide surface can be doped to promote CH bond activation that is important in oxidative dehydrogenation reactions. We show that when many reaction channels are possible in an undoped oxide surface, doping increases the selectivity by facilitating a particular reaction channel while suppressing others.