Water-gas shift reaction was carried out over a series of CuO/CeO2 catalysts doped with trivalent rare earth oxide (RE2O3, RE = Y, La, Nd and Sm), prepared via co-precipitation method. The effect of the dopants on the structure and catalytic properties of CuO/CeO2 catalysts was investigated with the aid of X-ray diffraction (XRD), Raman spectra, N-2 physisorption, H-2-TPR and selective N2O chemisorption characterizations. The results reveal the beneficial role of La2O3 and Nd2O3 doping in increasing the WGS catalytic activities and stabilities of CuO/CeO2 catalysts, while the addition of Y2O3 and Sm2O3 leads to the negative effect. Correlating to the characteristic results, it is found that the performance of CuO/CeO2-RE2O3 catalysts strongly depends on their surface copper dispersion, microstrain value and the amount of oxygen vacancies generated in ceria lattice. Besides, enough evidences suggest that, the most effective active site for WGS reaction is the moderate copper oxide (crystalline) interacted with surface oxygen vacancies of ceria in the CuO-CeO2 system. (C) 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.