In this paper, AlOOH samples were prepared by precipitation method, sol-gel hydrothermal method and hydrothermal method separately.These samples were characterized by XRD, BET, FT-IR, NH3-TPD-MS and CO2-TPD-MS.At the same time, the catalytic performance of AlOOH and C302 composite catalysts, loaded by layers in a fixed bed reactor, was evaluated in CO hydrogenation reaction.Evaluation results show that the different preparation methods of AlOOH dramatically affected the product distribution of the layered composite catalyst.Among them, precipitation method was beneficial to the formation of dimethyl ether, while the hydrothermal method was conducive to the production of higher alcohols.Related characterization results show that the crystallinity of AlOOH was improved after hydrothermal treatment.Besides, AlOOH with complete crystal forms, obvious preferred orientation, and appropriate acidicbasic sites favored the formation of higher alcohols.This study provides a new way for synthesis of higher alcohols from syngas.