The adsorption of O2 on Cu/CeO2(111) and the CO oxidation reactivity of the formed oxygen species were studied using the DFT method. The results showed that superoxide species (O2δ-), which directly interacted with Cu, formed when O2 adsorbed on the surface oxygen vacancies, while O2 adsorbed on the subsurface oxygen vacancies gave rise to ozone-like O3δ- species by combining with the nearest surface lattice oxygen (O1). PDOS showed that hybridization of the 2p orbitals between O2 and O1 formed a delocalized π bond, confirming the formation of O3δ-. For O2δ-, electrons on Cu and O1 transferred to O2 while the charge of Ce remained unchanged. However, for O3δ-, the transferred electrons were mainly from O1, and partially from O2, Ce1 and Ce2. It was very interesting that Cu also received a few electrons in the latter case. Compared with CO directly adsorbed on lattice oxygen, the two oxygen species were active for CO oxidation, forming CO2 or carbonates, and higher absolute adsorption energy was obtained with the interaction between CO and O3δ-. The findings of this study provide new insight on the CO oxidation reaction mechanism, facilitating an in-depth understanding of Cu-doped CeO2 catalysts.