Thermal catalytic technology is a significant and priority method to realize the industrial application of CO2 resource utilization, and the appropriate catalyst is particularly critical. Herein, Fe–Co bimetallic catalyst and Fe–Co–Ni trimetallic catalyst were prepared with the corresponding MOFs as precursors, aiming to find out the significant role of the Ni component in thermal catalytic CO2 reduction. Different kinds of characterizations revealed that the introduction of Ni resulted in more and smaller highly dispersed metal particles, the lower collapse degree of polyhedral morphology, and the improved reduction degree of the initial catalyst. Therefore, the adsorption capacity for the reactant gas was strengthened, and more basic sites for the excitation of CO2 were present, enhancing the RWGS reaction activity and the C–C bond coupling activity to generate more C2+ hydrocarbons. As a result, compared to the Fe–Co bimetallic catalyst, the addition of Ni promoted CO2 conversion and the selectivity of C2–C4 products were significantly improved under proper proportions. Especially, among all catalysts, FCN-311, which represents the mole ratio of Fe:Co:Ni as 3:1:1, exhibits the highest C2–C4 selectivity of 78% with a CO2 conversion of 51%.Graphical Abstract: