Abstract: The catalyst CuCo/γ-Al₂O₃ was prepared by coimpregnation and modified by glow discharge plasma, and then characterized by XRD, HOT, CO-TPD, and TPR. The performance of the plasma modified catalyst for CO hydrogenation to higher alcohols was investigated. The results showed that the plasma modification obviously promoted the dispersion of active species and caused the enrichment of active components on the catalyst surface. Meanwhile, the plasma treatment modified the interaction between the active species; the amount of strongly adsorbed CO on the catalyst surface was then increased remarkably. The catalytic performance of CuCo/γ-Al₂O₃ for higher alcohols synthesis was also enhanced by the plasma modification; the conversion of CO and the space time yield of higher alcohols over the plasma modified catalyst were higher than those over the catalyst prepared by the conventional impregnation method.