The optical basicity Lambda of metallic oxides is obtained by a linear combination of the optical basicity of cations and depends on their valence, coordination and spin state. Lambda quantifies the electron donor/acceptor power of the solid, which may be correlated with its redox properties. During catalysis, it is expected that the electron donor/acceptor property of the selective catalyst matches the acceptor/donor property of the reactant to be selectively transformed into the product. The selectivity is accounted for by Delta I which is the difference between the ionization energies of reactant and product. Each selective catalyst/reactant-product couple is characterized by (Lambda, Delta I) value. Linear relationships between the (Delta I, Lambda) obtained for various catalyst/reaction couples are drawn for several types of selective oxidation reactions: mild oxidation of alkanes, of olefins and of alcohols, ammoxidation of hydrocarbons. total oxidation of alkanes and of olefins.