A series of CuCoMg nanosheets derived from the LDH precursor were prepared by co-precipitation (CP) strategy and evaluated for the production of ethanol and higher alcohols via CO hydrogenation. The CuCoMg catalyst with a moderate amount of magnesium demonstrated a relatively higher total alcohol selectivity of 46.9%, and the molar percentage of ethanol was 38.5% among the total alcohols. Based on XRD and HRTEM characterizations, the introduction of Mg into the CuCo catalytic system prominently improved the dispersibility of CuCo nanoparticles. More importantly, XPS and in situ CO DRIFT results confirmed the presence of activated surface hydroxyl groups derived from MgO species over the reduced CuCoMg catalyst, which involved in the formation of bicarbonate (b-HCO3-) species. It was conducive to the enhancement of the amount of CHx intermediates on the CuCoMg catalyst surface, which were applied to the CO insertion to synthesize ethanol rather than coupling to produce hydrocarbons in the CO hydrogenation reaction.