Two series of Cu–Ce–O and Cu–Co–Ce–O catalysts were prepared by co-precipitation method. The prepared catalysts were characterized by XRD, IR, TPR, XPS, BET and ICP-AES. The catalytic activities of the catalysts for low-temperature CO oxidation were evaluated through a microreactor-GC system. TPR results indicate that the addition of cobalt to the Cu–Ce–O can increase the dispersion of copper oxide, and the interaction between cobalt and copper can enhance the reducibility of each other. XPS analysis show that Ce4+, Cu2+, along with Co3O4, are present on the surface of Cu0.4Co0.6Ce4 catalyst. The Co/Cu atomic ratio and the calcination temperature have significant effect on the activities of the catalysts. Compared with Cu1Ce4 catalyst, the Cu0.4Co0.6Ce4 catalyst has better activity and thermal stability.