The purpose of this study was to investigate the effect of the preparation method on CeO2-promoted Cu/γ -Al2O3 catalysts for the high temperature shift reaction using simulated waste-derived syngas (H2 + CO). To investigate the effect of preparation method on the CeO2-promoted Cu/γ-Al2O3 catalyst, we compared catalytic performance over Ce/Cu/γ-Al2O3, Ce-Cu/γ-Al2O3, Cu/Ce/γ-Al2O3, and Cu/γ-Al2O3 catalysts, and tried to explain the differences in catalytic performance with various characterization methods. The physico-chemical properties of the CeO2-promoted catalysts were characterized using surface spectroscopies such as BET, XRD, TPR, XPS, Raman spectroscopy, photoluminescence spectroscopy, and N2O-chemisorption. The catalyst characterizations were correlated with activity results in the high temperature shift reaction.