Low-temperature oxidation of CO, perhaps the most extensively studied reaction in the history of heterogeneous catalysis, is becoming increasingly important in the context of cleaning air and lowering automotive emissions. Here, we have studied low-temperature CO oxidation on Co(0001) using temperature programed desorption method. We show that chemisorbed O adlayer on Co(0001) does not promote CO2 formation. However, when a Co3O4-like surface is formed at 90 K, large amount of CO2 is produced at 90 K in the presence of weakly bound oxygen species, demonstrating that lowtemperature CO oxidation can be rationalized on O-2-saturated Co3O4-like oxide surfaces. However, the formation of carbonate species via the CO2 product and weakly bound oxygen species reduces the yield of low temperature CO2. Thus, how to block the formation of carbonate plays a key role in enhancing the low-temperature CO2 production on the Co3O4-like oxide surfaces. (C) 2017 Elsevier B.V. All rights reserved.