Conversion of CO2 by hydrogenation into higher hydrocarbons has attracted much attention due to the continuous increasing concentration of CO2 in the atmosphere. Fe5C2 was used as the active site and mixed with K-modified supports for CO2 hydrogenation to synthesize value-added hydrocarbons, A series of supports were tested, and the alkaline Al2O3 was the best choice for light olefins and C5+ hydrocarbons. The transformation of product selectivity at time on stream demonstrated that potassium inigrated into Fe5C2 during reaction. The selectivity of C2+ is 69,296 containing 3.896 C-2-C-4(=) and 29.1% C5+ value-added hydrocarbons with the 31.5% CO2 conversion ((H-2/CO2 = 3), When the ratio of H-2 and CO2 was switched to 4, CO2 conversion improved to 40,9%, and the C2+ selectively containing 37.3% C-2-C-4(=) arid 31.1% C5+ value-added hydrocarbons The mixture catalysts can be directly used reduction before reaction, reducing the consumption H-2 and simplifying the operation.