Abstract The directed synthesis of linear α ‐olefins (LAOs) from CO 2 and renewable green hydrogen is important for increasing the yield of LAOs and realizing the CO 2 resource utilization. Here, we report a K‐FeZr catalyst with a FeZr–Fe 5 C 2 interface, which exhibited excellent performance at 320°C, 1.5 MPa, and 7500 mL·g cat −1 ·h −1 , with a 13.0% LAOs yield and achieving a 39.1% CO 2 conversion. The characterization results indicated that the FeZr–Fe 5 C 2 interface significantly improved the catalytic activity through a multicomponent synergistic effect. The oxygen vacancies on the surface of the ZrO 2 support effectively anchored the Fe species, and the K promoter enhanced the carburization capacity of Fe and the dissociation of CO. The FeZr component exhibited strong adsorption capacity for the reactants and key intermediates, which promoted the C‐C coupling on the Fe 5 C 2 active site. These findings will contribute to the development of new and efficient catalysts for CO 2 hydrogenation.