Cu nanoclusters supported on Co nanosheets (denoted Cu/Co) were prepared using lysine as a surfactant template. The shape of the Cu/Co catalyst promotes selective hydrogenation of CO, enhancing CO conversion and the selectivity for higher alcohols, and decreasing methane selectivity, which is in marked contrast to current Cu–Co bimetallic nanoparticle catalysts. The distinct functional interface of the Cu(111) surface with face-centered cubic structure with the Co(100) surface with hexagonal closed-packed structure in the Cu/Co catalyst provides a breakthrough in understanding the catalytic nature of metal-metal interactions. The design of this bimetallic catalyst bridges the gap between model catalysts and realistic catalytic applications, and will ultimately allow us to gain a fundamental understanding of the mechanism of syngas conversion to higher alcohols.