A series of Mg-Al-Ce mixed oxides with (nMg(2+))/(nCe(3+) + nAl(13)+) = 5 and nCe(3+)/(nCe(3+) + nAl(3+)) = 0 similar to 7% were synthesized by co-precipitation method based on a hydrotalcite route and used as support to prepare Co-Mo sulfur-resistant water-gas shift (WGS) catalysts. The supports and catalysts were characterized by XRD, ICP, N-2- physisorption; CO2-TPD, H-2-TPR, H2S-TPS, TEM, and CO-IR. It is found that the catalytic performance and physicochemical property of the Co-Mo/Mg(AI)O catalyst are significantly influenced by the Ce modification. The addition of Ce effectively enhances the WGS activity and the highest activity is obtained on the Co-Mo/Mg (Al)O-CeO2 (5%) catalyst, where the activity at 623 K increases about 2.5 times. The results of H2S-TPS investigation show that in the presence of Ce, the H2S consumption peak shifts to lower temperatures and there is decrease of Mo sulfidation activation energy. Furthermore, HRTEM analysis shows that the addition of Ce (5%) results in decrease of MoS2 slab length and stacking number, and those of CO-IR characterization indicate increased exposure of surface MoS2 sites. It is suggested that the addition of Ce promotes the formation of MoS2 slabs that are smaller in size, leading to higher exposure of surface active sites and hence higher activity.