In this paper, Ni/Zr–Yb–O catalysts with different sodium contents are prepared by a co-precipitation method, using aqueous Na2CO3 solution as a precipitant, and the effect of sodium on the catalyst structure and catalytic perfor-mance for syngas methanation is extensively investigated using five Ni/Zr–Yb–O catalysts, containing 0, 0.5, 1.5, 4.5 and 13.5 wt％Na+, those are denoted as Cat-1, Cat-2, Cat-3, Cat-4 and Cat-5 respectively. It is found that the in-teraction between Ni and support determines the catalytic performance of Ni/Zr–Yb–O and the residual sodium content negatively affects the interaction between Ni and support. Cat-1 exhibits an excellent catalytic performance. During a long run time of 380 h, no deactivation is observed and both CO conversion and CH4 selectivity maintain a level above 90％. However, Cat-3 and Cat-5 suffer rapid deactivation under the same reaction condition. The charac-terization results indicate the strong interaction between Ni and support enables Cat-1 to possess well dispersed Ni species, resistance to sintering and carbon deposition and thus the excellent catalytic performance. However, the presence of sodium ions over Ni/Zr–Yb–O degrades the interaction between Ni and support and the catalytic perfor-mance, especially for the stability. The relative weak interaction between Ni and support results in severe sintering of both ZrO2 and Ni under the reaction condition, carbon deposition and the poor catalytic performance.