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Methods for the identification of the nature and source of the two catalytic functions, the acidic and oxidative properties, of the heteropoly oxometalates are reviewed and discussed. The use of both the supported and unsupported heteropoly oxometalates as catalysts in acidity-requisite processes ranging from methanol conversion to hydrocarbons to ring-expansion and contraction processes and in oxidation processes from methane cyclohexane are described and related to the aforementioned properties.