CuOx/CeO2 catalysts were prepared by adsorption-impregnation method, CO conversion was tested over the catalysts pretreated under different conditions for preferential CO oxidation in H2, and the catalysts were characterized with X-ray photoelectron spectroscopy and temperature programmed reduction. Experimental results show that there are two kinds of copper, which are Cu^+ and Cu^2+ in calcined CuOx/CeO2, Among them, the Cu^+ is the key active component for CO oxidation. The main reason is as follows: CO is activated by copper for CO oxidation over CuOx/CeO2, while CO can not be activated by Cu^2+. Only when Cu^2+ is reduced to Cu ^+ or Cu^0, the copper may be active for CO oxidation, moreover, the experimental results show that the reduction of Cu^2+ does not lead to an increase of catalytic activity. So the active species is Cu^+ in CuOx/CeO2 catalysts.