The search for substitutes of noble metal supported exhaust control catalysts has led to the study of a number of perovskite oxides (1). The mechanisms of redox processes on these surfaces are topotactic in nature, thus accounting forthe reversible loss and uptake of bulk oxygen or for the concomitant creation and annihilation of vacancies rendering these systems as attractive oxidation catalysts. The variable oxygen stoichiometry of perovskite structure is responsible for the exotic behavior of these materials as a new class of high Tc superconducting oxides (2). The extreme ease of removing oxygen from the framework but still retaining the basic ingredients of the perovskite structure and the possibility of deriving different structural frameworks from ideal perovskite structure (e.g. insertion of rock salt layer between perovskite layers results in a K2NiF4structure, while insertion of double [Bi2O2] layers between perovskite layers results in an Aurivillius phase) and the possibility of substitution of either or both A and B site cations by foreign metal ions make them function as chemical chameleons (3) with a wide variety of solid state and catalytic properties. Among the various redox catalytic processes promoted by them the oxidation of CO and the reduction of NO seem to be interesting in view of their relevance for auto-exhaust emission control. The present chapter attempts to consider the generalities that have been evolved in these studies, which will be useful for the formulation of auto-exhaust control catalysts based on perovskites in the future.