Nanostructured CuCo-LDH/CNT composites were successfully synthesized according to the co-precipitation method and firstly used for higher alcohol synthesis. The structural characterization and morphological observation demonstrated that CuCo-LDHs were in situ grown on the CNTs surface, and the CNTs support favored the dispersion of LDHs; meanwhile, a mechanism for growing the LDHs on CNTs was proposed, and the reported methods could be expanded to prepare other LDHs/CNT composites. After reduction, due to the strong interaction between CuCo-LDHs and CNTs, Cu-Co alloy, nanoparticles with small and uniform size were obtained and highly dispersed on the Al2O3 matrix and CNTs surface. In particular, the high thermal conductivity of CNTs suppressed the formation of hot spots, thus effectively inhibited the generation of hydrocarbons and CO2. The resultant CuCo-LDHs/CNTs composite exhibited better catalytic performance and higher selectivity to C2+ alcohols than the pristine LDHs did, which turned out to be one of the best catalysts for HAS.