Correlations between the electronic and chemical properties of perovskites, molybdates, and metal-doped MgO or CeO2 are examined. Simple models based on band-orbital mixing can explain trends found for the interaction of these catalytic materials with adsorbates: the less stable the occupied levels of a mixed-metal oxide, the higher its chemical reactivity. Metal <----> oxygen <----> metal interactions are common in mixed-metal oxides and can lead to substantial changes in the electronic and chemical properties of the cations. This is particularly true in the case of ABO(3) perovskites (A = Pb, Ca, Sr, Li, K, Na; B = Ti, Zr, Nb), and it is an important phenomenon that has to be considered when mixing AO and BO2 oxides for catalytic applications. In systems like Ce1-xZrxO2 and Ce1-xCaxO2, the structural stress induced by the dopant (Zr or Ca) leads to perturbations in the electronic properties of the Ce cations. The trends in the behavior of metal-doped MgO illustrate a basic principle in the design of mixed-metal oxide catalysts for DeNO(x), and DeSO(x) operations. The general idea is to find metal dopants that upon hybridization within an oxide matrix remain in a relatively low oxidation state and at the same time induce occupied electronic states located well above the valence band of the host oxide. Electronic effects should not be neglected a priori when explaining the behavior or dealing with the design of mixed-metal oxide catalysts. (C) 2003 Elsevier B.V. All rights reserved.