The role of the catalyst surface acid-base properties on the heterogeneously-catalyzed oxidation reaction mechanisms is discussed. Acid-base properties depend on the covalent/ionic character of the metal-oxygen bonds and are involved in some steps of the oxidation reactions, such as the activation of the C-H hydrocarbon bonds, the step associated with the evolution of alkoxide species and the desorption/overoxidation of the partial oxidation products. Thus they participate with the cation redox properties in determining the selective/unselective catalyst behavior.