Currently, direct catalytic CO 2 hydrogenation to produce ethanol is an effective and feasible way for the resource utilization of CO 2 . However, constructing non-precious metal catalysts with satisfactory activity and desirable ethanol selectivity remains a huge challenge. Herein, we reported gallium-promoted CuCo-based catalysts derived from single-source Cu-Co-Ga-Al layered double hydroxide precursors. It was manifested that the introduction of Ga species could strengthen strong interactions between Cu and Co oxide species, thereby modifying their electronic structures and thus facilitating the formation of abundant metal-oxide interfaces ( i.e. , Cu 0 /Cu + -CoGaO x interfaces). Notably, the as-constructed Cu-CoGa catalyst with a Ga:Co molar ratio of 0.4 exhibited a high ethanol selectivity of 23.8% at a 17.8% conversion, along with a high space-time yield of 1.35 mmol EtOH ·g cat -1 ·h -1 for ethanol under mild reaction conditions ( i.e. , 220 °C, 3 MPa pressure), which outperformed most non-noble metal-based catalysts previously reported. According to the comprehensive structural characterizations and in situ diffuse reflectance infrared Fourier transform spectra of CO 2 /CO adsorption and CO 2 hydrogenation, it was unambiguously revealed that CH x could be formed at oxygen vacancies of defective CoGaO x species, while CO could be stabilized by Cu + species, and thus the catalytic synergistic role of Cu 0 /Cu + -CoGaO x interfacial sites promoted the generation of CH x and CO intermediates to participate in the CH x -CO coupling process and simultaneously inhibited alkylation reactions. The present work points out a promising new strategy for constructing CuCo-based catalysts with favorable interfacial sites for highly efficient CO 2 hydrogenation to produce ethanol.