Ce-promoted NiMgAl mixed-oxide (NiCex-C, x = 0, 1, 5, 10) catalysts were prepared from the quaternary hydrotalcite precursors for CO2hydrogenation to methane. By engineering the Ce contents, NiCe5-C showed its prior catalytic performance in low-temperature CO2hydrogenation, being about three times higher than that of the Ce-free NiCe0-C catalyst (turnover frequency of NiCe5-C and NiCe0-C: 11.9 h−1vs. 3.9 h−1@ 225 °C). With extensive characterization, it was found that Ce dopants promoted the reduction of NiO by adjusting the interaction between Ni and Mg(Ce)AlOx support. The highest ratio of surface Ni0/(Ni2++ Ni0) was obtained over NiCe5-C. Meanwhile, the surface basicity was tailored with Ce dopants. The strongest medium-strength basicity and highest capacity of CO2adsorption was achieved on NiCe5-C with 5 wt.% Ce content. The TOF tests indicated a good correlation with medium-strength basicity over the NiCex-C samples. The results showed that the high medium-strength and Ce-promoted surface Ni0species endows the enhanced low-temperature catalytic performance in CO2hydrogenation to methane.