In this paper, the structure-activity relationship of three AlOOH samples prepared using the complete liquid-phase, hydrothermal and precipitation methods is investigated. The structure of AlOOH samples is characterized by XRD, BET, FT-IR, and NH3/CO2/CO-TPD-MS techniques. The activity of CO hydrogenation is studied over AlOOH composite catalysts which are mechanically mixed with a methanol synthesis catalyst, in a fixed-bed reactor. The results demonstrate that the different preparation methods employed have a profound effect on the structure of AlOOH, which subsequently affects the catalytic performance, especially the product distribution. Particularly, the AlOOH prepared using the hydrothermal method exhibits high crystallinity, and possesses an integrated interlayer structure. This unique structure enhances the dissociative adsorption of CO molecules, facilitates the growth of the carbon chain, and results in a remarkable increase in the proportion of higher alcohols in the products. Therefore, these findings contribute not only to a better understanding of catalysts for higher alcohols but also broaden the research scope in the field of catalytic material.