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Oxidative dehydrogenation of KA-oil (a mixture of cyclohexanone and cyclohexanol) is an economically attractive process to produce cyclohexanone because it provides a chance to avoid the energy-intensive alcohol-ketone separation process. The application of this process, however, is hampered by the low cyclohexanone selectivity which results from the competitive adsorption of cyclohexanol and cyclohexanone on the catalyst surface. Herein, by engineering Pt-Bi₂O₃ interface to tune the geometric and electronic structure of Pt, we successfully weaken the cyclohexanone adsorption without compromising the oxidation of cyclohexanol. As a result, Bi₂O₃-Pt/SiO₂ with Bi-to-Pd ratio of 0.2 exhibits a 5 times higher cyclohexanone selectivity than Pt/SiO₂ at the same conversion of KA oil. Long term test suggests that the Pt-Bi₂O₃ interface is stable in the oxidative dehydrogenation of KA-oil.