A type of novel MWCNT-supported Ni-Mo-K catalysts for higher alcohol synthesis (HAS) from syngas was developed, which displayed excellent performance for the selective formation of C1-3-alcohols and DME from syngas. Over the 15% Ni1Mo1K0.05/CNTs catalyst under the reaction conditions of 5.0 MPa and 538 K, the C-based selectivity of (C1-3-alc. + DME) reached 59.0%, with the corresponding STY of 205 mg h(-1) g(-1). This value was 1.16 times that of the 35% Ni1Mo1K0.05/AC catalyst with the optimal Ni1Mo1K0.05 loading, and 1.76 times that of the non-supported co-precipitated Ni1Mo1K0.05 host system, under the same reaction conditions. The results of the catalyst characterizations revealed that the CNT-support has strong influence on the chemical states of catalyst via its interaction with the supported Ni-Mo components, leading to the increase of the molar percentage of NiO(OH) and Mo4+/Mo5+ (the two kinds of catalytically active surface-species related closely to selective formation of C1-3-alcohols) and the dramatic decrease of the molar percentage of Ni-0 and Mo-0 (the two kinds of catalytically active surface-species related closely to selective formation of hydrocarbons, especially methanation of CO). Moreover, the CNT-support also provided the sp(2)-C surface-sites for adsorption-activation of H-2. All these factors contribute to an increase in selectivity of generating C1-3-alcohols.