The rational design of efficient Earth-abundant electrocatalysts for the ethanol oxidation reaction (EOR) is the key to developing direct ethanol fuel cells (DEFCs). Among these, the smart structure is highly demanded for highly efficient and stable non-precious electrocatalysts based on transition metals (such as Ni, Co, and Fe). In this work, high-performance NiCo-layered double hydroxide@carbon nanotube (NiCo-LDH@CNT) architectures with hollow nanocage structures as electrocatalysts for EOR were prepared via sacrificial ZIF-67 templates on CNTs. Comprehensive structural characterizations revealed that the as-synthesized NiCo-LDH@CNTs architecture displayed 3D hollow nanocages of NiCo-LDH and abundant interfacial structure between NiCo-LDH and CNTs, which could not only completely expose active sites by increasing the surface area but also facilitate the electron transfer during the electrocatalytic process, thus, improving EOR activity. Benefiting from the 3D hollow nanocages and interfacial structure fabricated by the sacrificial ZIF-67-templated method, the NiCo-LDH@CNTs-2.5% architecture exhibited enhanced electrocatalytic activity for ethanol oxidation compared to single-component NiCo-LDH, where the peak current density was 11.5 mA·cm-2, and the jf/jb value representing the resistance to catalyst poisoning was 1.72 in an alkaline environment. These results provide a new perspective on the fabrication of non-precious metal electrocatalysts for EOR in DEFCs.