Abstract: AlOOH were prepared by precipitation-hydrothermal method with different water-to-gel ratios, which were mixed with industrial methanol synthesis catalyst C302 and tested for CO hydrogenation in the fixed-bed reactor. The AlOOH samples were characterized by XRD, FT-IR, BET, NH₃-TPD-MS, TG-DTG and H₂-TPR. The results showed that the ratios of water-to-gel in the hydrothermal process had obvious influence on the preferred orientation, pore structure and surface acidity of AlOOH, leading to the different selectivity of higher alcohols and DME. When the ratio of water-to-gel was 2:1, AlOOH showed in (020) and (120) preferred orientation. Moreover, it had larger pore volume and proper ratio of weak acid sites to strong acid sites, the composite catalyst showed a relatively high selectivity of higher alcohols, which indicated that AlOOH favored the growth of carbon chains. This study provided a new way for synthesis of higher alcohols from syngas.