Bimodal support modified Cu-Fe based catalysts with different pore structures were prepared and tested for higher alcohols synthesis (HAS). It was found that the bimodal derived catalyst showed both higher catalytic activity and selectivity of C2 +OH compared to the traditional Cu-Fe based catalysts. In particular, both the activity and C2 +OH selectivity presented an increasing trend with the gradual decrease in bimodal support pore sizes. The characterization results indicated that decreasing support pore sizes resulted in the increase of BET surface area and dispersion of active Cu and Fe species inside the pore structures, which increased the bimetallic active sites and strengthened probably the synergistic effect of Cu-Fe via “confine effect” of bimodal pore structures, improving the HAS catalytic activity and shifting product distribution towards higher alcohols.