With regard to the reaction of higher alcohol synthesis (HAS), the optimizations of activity and selectivity towards C2+alcohol are restricted by the improper equilibrium in two different CO activation pathways and chain growth capacity. Herein, we find that delibrately controlling the compositions of catalysts is an effective strategy to achieve the equilibrium of CO activation pathways and promote the chain growth. As a result, the optimized Cu0.25Co0.75 alloy catalyst can achieve a large proportion of higher alcohol in alcohol products (C2+OH/MeOH=4.40), together with high CO conversion of 71.27％and space-time-yield of 147.65 g kg 1 h 1. The mechanistic studies suggest that the good performance of Cu0.25Co0.75 catalyst is attributed to the synergistic effect between alloyed Cu and Co.