A kind of K-Co-Mo catalyst with large surface area, small particle size and homogenous components distribution was prepared by sol-gel method using citric acid as complexant, and characterized by XRD, BET, HR-TEM, EXAFS and TPD techniques. The activity for mixed alcohol synthesis from syngas on the catalysts was investigated. During the preparation, a gelation process was adopted to prevent the components from precipitating during the solvent extraction and keep the homogeneity and small particle size of final products. Heat-treated the dried gel in argon, the decomposition of critic acid partly reduced the sample and decreases the particle sizes remarkably. The synthesized K-Co-Mo catalyst exhibited excellent performance for mixed alcohol synthesis from CO hydrogenation, which may be due to its large surface area and small particle size creating more active sites. Beside it, the homogeneity of various components was also helpful to enhance the synergistic effect of Co promoters. The high selectivity to the C 2+ OH was due to the large amount of SH species adsorbed on the catalyst surface.