The specific synthesis of ethanol from syngas is particularly important for C1 chemistry platforms. Herein, the uniformly decorated xLa/SiO₂-supported CuCo catalysts were prepared by a facile incipient wetness impregnation (IM) method. On the basis of detailed characterization and catalytic performance, the relationship between the distribution of active Cu and Co species and intrinsic catalytic activity was established and discussed. The La₂O₃ preferentially enhances the dispersion of copper and inclines to generate stable Cu⁺ from Cu-O-La units. Additionally, SiO₂ is conducive to the generation of Cu⁰, and then promotes the reduction of adjacent Co²⁺ to Co⁰ through hydrogen spillover. It was found that the CuCo/(5La/Si) catalyst showed a highest CO conversion of 44.2% and the space time yield of total alcohols (STY_ROH) of 61.6 mg/mL_cat·h, which was 8.0-fold and 3.3-fold higher than that of undecorated CuCo/(Si) catalyst, respectively. Moreover, a superior ethanol selectivity in total alcohols is as high as 34.0 wt%. The significant improvement in catalytic performance is attributed to the abundant Cu⁺-Co⁰ in the interface with strong capacity on C–C chain growth. This work provides a novel and simple model for the rational design other related CuCo catalyst with beneficial performance, which is of great significance to reveal the unique synergistic interface between Cu and Co species.