CO2　hydrogenation　is　an　effective　solution　for　direct　ethanol　production　as　it　realizes　a　high-value　utilization　of　waste　CO2.　As　it　requires　a　synergistic　multi-step　process　of　CO2　activation,　asymmetric　hydrogenation　of　CO,　and　precise　coupling　of　C-C　bonds,　the　design　of　highly　active　and　selective　catalysts　for　such　procedures　remains　challenging.　In　this　study,　we　prepared　a　series　of　La-doped　CuFe　catalysts　using　a　simple　and　green　solvent-free　ball　milling　method　to　accelerate　the　rate　of　CO2　hydrogenation　to　ethanol　generation.　HRTEM,　in　situ　XRD,　EPR,　and　CO2-TPD　analyses　indicated　that　the　doping　of　moderate　amounts　of　La　can　significantly　improve　the　dispersion　of　the　Cu　and　Fe　species,　enhance　the　interaction　between　the　CuFe　species,　decrease　the　reduction　temperatures　of　CuO　and　Fe2O3,　promote　the　formation　of　oxygen　vacancies　during　the　reaction　process,　and　enhance　CO2　adsorption　and　activation　ability.　DFT　calculations,　XPS,　in　situ　FTIR,　and　CO-TPSR-MS　analyses　indicated　that　the　transfer　of　electrons　from　the　Fe　to　La　species　decreased　their　electron　cloud　densities,　weakened　the　bridge　type　adsorption　of　CO,　enhanced　the　linear　adsorption　of　CO,　and　optimized　the　ratio　of　the　dissociative　and　non-dissociative　adsorption　of　CO　intermediates,　which　ultimately　resulted　in　a　better　matching　of　the　rates　of　generation　of　CHx*　and　C(H)O*　intermediates.　The　occurrence　of　C-C　coupling　at　the　abundant　Cu0-Fe5C2　interface　promoted　the　highly　efficient　synthesis　of　ethanol,　achieving　yields　as　high　as　13.5%　over　the　5La-CuFeOx　catalyst,　ranking　the　top　level　among　the　reported　catalysts　in　the　literature.　This　study　presents　a　feasible　strategy　for　the　targeted　regulation　of　multicomponent　active　centers.　©　2024　Elsevier　B.V.