Abstract: A new Co/La₂O₃-La₄Ga₂O₉ catalyst was prepared by reducing LaCo_1-xGa_xO₃ perovskite and used in the direct synthesis of ethanol from CO₂ hydrogenation. The composite catalyst was characterized by XRD, XPS, TPD and TEM and its catalytic performance in CO₂ hydrogenation was investigated in a micro fixed-bed reactor operated at 230-290℃, 3 MPa, gas hourly space velocity (GHSV) of 3000 mL/(g_cat·h) and H₂/CO₂ molar ratio of 3.0. The results indicate that the Co/La-Ga-O composite oxide catalyst exhibits high selectivity to ethanol in CO₂ hydrogenation. In comparison with the LaCoO₃ catalyst, the incorporation of Ga dopant can inhibit the formation of CH₄ and then promote the production of alcohols, especially ethanol. With a Co/Ga atomic ratio of 7:3, the Co/La-Ga-O composite oxide catalyst displays the best performance in CO₂ hydrogenation, with a CO₂ conversion of 9.8%, a selectivity of 74.7% to total alcohols and ethanol content of 88.1% (mass ratio) in the alcohols mixture. On the basis of the experimental results, it is speculated that the synergistic effect of surface Co⁰ and Co^δ+ may contribute to the excellent performance of the Co/La₂O₃-La₄Ga₂O₉ catalyst in CO₂ hydrogenation to ethanol.