Durable, highly efficient, and economic sound electrocatalysts for CO electrooxidation (COE) are the emerging key for wide variety of energy solutions, especially fuel cells and rechargeable metal−air batteries. Herein, we report the novel system of nickel−aluminum double layered hydroxide (NiAl-LDH) nanoplates on carbon nanotubes (CNTs) network. The formulation of such complexes system was to be induced through the assistance of gold nanoparticles in order to form dual-metal active sites so as to create a extended Au/NiO two phase zone. Bis(trifluoromethylsulfonyl)imide (NTf₂) anion of ionic liquid electrolyte was selected to enhance the CO/O₂ adsorption and to facilitate electro-catalyzed oxidation of Ni(OH)₂ to NiOOH by increasing the electrophilicity of catalytic interface. The resulting neutral catalytic system exhibited ultra-high electrocatalytic activity and stability for CO electrooxidation than commercial and other reported precious metal catalysts. The turnover frequency (TOF) of the LDH-Au/CNTs COE catalyst was over 70 times higher than the previous reported other similar electrocatalysts, even close to the activity of solid-gas chemical catalysts at high temperature. Nonetheless, in the long-term durability testing, the negligible variation of current density remains exsisting after 1000 electrochemistry cycles.