Two series of supported Co-based catalysts were prepared using a facile co-impregnation method. The catalysts were examined in a fixed bed for their ability to selectively convert syngas into higher alcohols. Co-Cu and Co-CeO2-x sites have an excellent synergistic effect, which could terminate the growth of the carbon chain effectively for the synthesis of alcohols. Furthermore, the Co-CeO2-x site is more beneficial for the synthesis of higher alcohols than the Cu-Co centre. The selectivity for the formation of ethanol and C-1-C-3 alcohols achieved using the 10Co5Ceicarbon nanotubes catalyst were 29.7% and 89.5%, respectively. In addition, the separation of the Co and CeO2-x sites weakens the synergistic effect, and thus, causes the formation of long chain hydrocarbons. The structure-performance correlation studies suggest that the geometric structure of the catalyst likely plays an important role in determining the formation of the Co-CeO2-x site, which influences the selectivity towards higher alcohols and higher aliphatic hydrocarbons. (C) 2017 Elsevier Ltd. All rights reserved.