We have developed selective oxidations of hydrocarbons catalyzed by various kinds of hydrotalcites. In this article, the catalytic features of the layered hydrotalcites in the heterogeneous hydrocarbon oxidations are reviewed. We discuss the active sites of the hydrotalcite catalysts for oxidations such as 1) the Baeyer-Villiger oxidation of various ketones using the combination oxidant of molecular oxygen and aldehydes or m-CPBA, and 2) the epoxidation of various olefins with hydrogen peroxide in the presence of nitriles. The heterogeneous catalyst systems using the hydrotalcites do not stress the environment because of using molecular oxygen and H₂O₂ as oxidants and of their strikingly simple work up; the hydrotalcites are easily separated from the reaction mixture and are reusable without an appreciable loss of activity and selectivity of the oxidation reactions.