This work demonstrates a new approach to preparing Cu-Co-based catalysts for higher alcohols synthesis from syngas. Oxidized multiwalled carbon nanotubes (MWNTs) were adsorbed onto silica gels, and MWNT-silica gels were used as the support of a Cu-Co-based catalyst. Pyrogallol was used in preparing the catalyst. It has been found that the carbon nanotubes in the support favor the distribution and interaction of Cu and Co species; using pyrogallol in preparing the catalyst improves the distribution of Cu and Co species and promotes the interaction between the species. As a result, the catalyst can decrease the methanol selectivity from 43.0% to 26.8% and increase the ethanol selectivity from 33.1% to 43.5%, in comparison to the catalyst, with silica gels as the support.