Transforming　CO2　into　heavy　hydrocarbons　via　thermal　catalytic　hydrogenation　has　garnered　interest　for　its　potential　to　address　resource　shortages　and　reduce　atmospheric　CO2.　In　this　research,　NaFeGa　catalysts　enriched　with　Ga　additives　were　synthesized　by　the　coprecipitation　method.　Various　characterization　techniques,　including　Mössbauer　spectroscopy,　were　employed　alongside　reverse　water-gas　shift　and　Fischer-Tropsch　synthesis　experiments　to　elucidate　the　Fe-Ga　interaction.　This　interaction　effectively　modulated　the　ratio　of　active　sites　Fe5C2　and　enhanced　CO　species　adsorption.　The　Ga　additive＇s　anti-hydrogenation　effect　limited　intermediate　hydrogenation,　leading　to　increased　carbon-hydrogen　product　yields.　The　catalyst　underwent　direct　hydrogenation　of　CO2　under　high　throughput　conditions　(space　velocity　of　50,000　h−1),　resulting　in　efficient　CO2　conversion　as　well　as　remarkable　heavy　hydrocarbon　selectivity.　The　catalyst　demonstrated　a　remarkable　heavy　hydrocarbon　space-time　yield　(STY)　of　1460.2　g·kgcat−1·h−1,　surpassing　the　threshold　for　commercial　viability　and　offering　a　promising　solution　for　large-scale　production　of　liquid　fuels　from　CO2.　©　2024　Elsevier　B.V.