A series of CuO/Ce0.6Zr0.4O2 catalysts doped with rare earth (Y, La) oxides and transition metal (Fe, Co, Ni) promoters were synthesized by the coprecipitation method. The effects of the additive type and content on the structure, redox properties, and water-gas shift (WGS) catalytic activity were investigated in detail by X-ray diffraction, N-2 physisorption, scanning electron microscopy, energy-dispersive X-ray spectroscopy, H-2 temperature-programmed reduction, and Raman spectroscopy. The catalytic activity was tested in terms of CO in H-2-rich coal-derived synthesis gas, which simulated the actual gas composition of an integrated gasification combined cycle system. The experimental results revealed the beneficial role of doping with 3wt% Fe in enhancing the catalytic performance by increasing the oxygen storage and mobility capacity, the reducibility, and the synergistic interaction between copper oxide and ceria-zirconia.