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A series of [Pd(NHC)(PR3)] complexes quantitatively form [Pd(η2-O2)(NHC)(PR3)] products when submitted to an dioxygen atmosphere. Synthetic details and structural features of these Pd–peroxo complexes are described. The palladium compounds were found to be efficient catalysts in the oxidation of alcohols into corresponding carbonyl compounds using O2 or air as oxidant. Reactions proceed at low catalyst loadings with a wide range of alcohols.