Abstract: Cu-Fe bimodal pore catalysts modified with basic metal additives for higher alcohols synthesis (HAS) were prepared by an ultrasonic impregnation method. The study was undertaken to investigate the effects of various basic metal additives on the microstructures and HAS performances of catalysts. Several techniques, including N2 physical adsorption, temperature programmed reduction of hydrogen, X-ray diffraction and X-ray photoelectron spectroscopy, were combined to characterize these catalysts. The characterization results indicated that bimodal pore support was formed with the addition of small pore silica sol into the macroporous silica gel. Adding additives containing Ca and Li into Cu-Fe bimodal catalyst increased the amount of CuO and decreased that of Fe2O3 on the surface layer of the catalyst, which could weaken the interaction of Cu-Fe-O and promote the formation of methanol. The addition of Na and K additives increased the amounts of copper and iron species on the surface layer, enhancing the synergistic effect of Cu-Fe and improving the HAS activity and selectivity of C2+OH. Among these four basic metal additives, catalyst with K additive exhibited the best activity and space time yield of higher alcohols.