A series of the Co-Zn catalysts supported on Mn-Al oxide with different Co/Zn molar ratios were synthesized according to the sol-gel method and used for higher alcohol synthesis from syngas. The chemical and physical properties of the as-synthesized catalysts were investigated by various characterization methods such as XRD, H-2-TPR, N-2 adsorption and desorption, CO2-TPD, CO-TPD, DRIFTS, H-2-TPD, TEM, XPS, and CO-TPSR. The results indicated that CO conversion and alcohol selectivity changed depending upon the Co/Zn molar ratio that significantly influenced the properties of the as-synthesized catalysts. The proper Co/Zn molar ratio can increase the concentration of moderate/strong basic sites, improve the amount of non-dissociated CO on the catalyst surface for CO insertion, and enhance the catalytic performance for higher alcohol synthesis. In particular, the 4Co-4Zn catalyst shows the highest selectivity to higher alcohols (80%) among all the catalysts.