In this paper, the CuO/Ce0.8Zr0.2O2 catalysts were prepared for the catalytic reduction of NO by CO. The structure and the redox behavior of these catalysts were investigated by using XRD and H-2-TPR. Three peaks (alpha, beta and gamma) are observed when H-2 is used as reducing agent. The a peak is attributed to the dispersed copper oxide, the beta peak is attributed to the moderate size bulk CuO and the y peak is attributed to the large size bulk CuO. The Cu loading and calcination temperature have effects on the catalytic activity for NO-CO reaction and the N2O selectivity. We conclude that the catalytic activity is related to the moderate size bulk CuO particles, and the N2O selectivity is related to the large size bulk CuO particles. The dispersed copper oxide does not contribute to the catalytic activity and N2O selectivity.