The structures and electronic properties of M x Ce 1−x O 2−δ (M=Au, Pd, Pt, and Rh) modeling catalysts were theoretically compared. Two kinds of active oxygen species were obtained by O 2 filling into or standing aside surface oxygen vacancy on M x Ce 1−x O 2−δ (111). Correspondingly, tridentate and bidentate carbonates form by CO reaction with the two different oxygen species. Finally, the possible oxidative activities of four M x Ce 1−x O 2−δ catalysts were evaluated by comparing the formation energy of surface oxygen vacancy, as well as the energy differences between carbonate and CO 2 desorption. Our work will provide important information for the design of catalyst with high oxidation performance.