In this paper, the effect of additive Fe on Ni/Al2O3 catalyst for CO2 methanation was studied. A series of bimetallic Ni–Fe catalysts with different Ni/Fe ratios were prepared by impregnation method. For comparison, monometallic Fe‐based and Ni‐based catalysts were also prepared by the same method. The characterization results showed that adding Fe to Ni catalyst on the premise of a low Ni loading(≦12 wt.%) enhanced CO2 methanation performance. However, when the Ni loading reached 12 wt.%, the catalytic activity decreased with the increase of Fe content, but still higher than the corresponding Ni‐based catalyst without Fe. Among them, the 12Ni3Fe catalyst exhibited the highest CO2 conversion of 84.3 % and nearly 100% CH4 selectivity at 50000 ml g‐1 h‐1 and 420 °C. The enhancement effect of adding Fe on CO2 methanation was attributed to the dual effect of suitable electronic environment and increased reducibility generated by Fe species.