XRD (X-ray diffraction), BET (Brunauer-Emmett-Teller), LRS (laser Raman spectra), XPS (X-ray photoelectron spectroscopy), and TPR (temperature-programmed reduction) are used to investigate the surface properties of CuO/WO3/Ce(0.5)Zr(0.5)O2 samples. The results indicate that (1) tungsten oxide can be highly dispersed on Ce(0.5)Zr(0.5)O2 (denoted as CZ hereafter) solid solution, with a dispersion capacity of about 0.8 mmol WO(3)/(100 m2 CZ), and comparatively, the supported tungsten oxide species are preferentially interacted with ceria component on the surface of CZ; (2) for CuO/WO3/CZ samples with a half-monolayer WO3 loading, i.e., xCu-0.4W-CZ series, the surface of CZ is only partially covered by the preloaded WO3) and the supported copper oxide species are dispersed on the remaining surface vacant sites on CZ as well as on top of the preloaded tungsten oxide, while for the samples preloaded with a full-monolayer WO3, i.e., xCu-0.8W-CZ series, only dispersed on the top of the preloaded tungsten oxide monolayer; (3) the effect of the loading amount of WO3 on the reduction property of Cu2+ ions in a series of CuO/WO3/CZ samples has been observed and tentatively attributed to the formation of WO3 monolayer on CZ and the different coordination environments of the dispersed Cu2+ ions are discussed on the basis of the consideration of the incorporation model proposed previously (Chen, Y.; Zhang, L. Catal. Lett. 1992, 12, 51).