Direct selective oxidation of light alkanes, such as ethane, into value-added chemical products under mild reaction conditions remains a challenge in both industry and academia. Herein, the iridium cluster and atomically dispersed iridium catalysts have been successfully fabricated using nanodiamond as support. The obtained iridium cluster catalyst shows remarkable performance for selective oxidation of ethane under oxygen at 100 degrees C, with an initial activity as high as 7.5 mol/mol/h and a selectivity to acetic acid higher than 70% after five in situ recycles. The presence of CO in the reaction feed is pivotal for the excellent reaction performance. On the basis of X-ray photoelectron spectroscopy (XPS) analysis, the critical role of CO was revealed, which is to maintain the metallic state of reactive Ir species during the oxidation cycles.