Improving the C₂₊ alcohols selectivity is the most difficult challenge in higher alcohol synthesis (HAS) from syngas. Herein, three effective strategies were combined to develop a Mo-based catalyst for HAS. The sol–gel method produced a highly homogeneous distribution of components, which ensured intimate and sufficient contact between different active sites. The incorporation of Mn oxide enhanced the interaction between Co and Mo and thus promoted the growth of the alcohol chain. More importantly, the reduction degrees of Co and Mo can be tuned precisely. The prepared Mn/K/Co/Mo catalysts show unusual activity for HAS.