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In this work, we investigate the catalytic performance of atomically monodisperse, thiolate-protected Au25(SR)18 (R=CH2CH2Ph) nanoclusters supported on CeO2.The solution phase Au25(SR)18 nanoclusters were directly deposited onto CeO2, and the as-prepared catalysts were evaluated for the CO oxidation reaction after pretreatment in O2 at different temperatures.