Zn-based materials are regarded as a family of promising electrocatalysts for electrochemical CO reduction reaction (e-CORR), especially for the CO-to-CO conversion. However, their electrocatalytic performances should be improved and the conversion mechanism needs to be further studied. In this work, we fabricate Cu-incorporated ZnO (CuZn-A) on Zn plate for e-CORR catalyst by a facile annealing method. We find that CuZn-A achieves a high CO Faraday efficiency > 90% with a CO yield rate of 0.49 mmol cm h. The improved catalytic activity on CuZn-A is mainly attributed to the Cu steps on the reconstructed surface in the reaction: (1) that weakens the OH/CO adsorption, leading to the anti-poisoning surface by preventing the formation of Zn hydroxide/carbonates; and (2) that enhances the adsorption/activation of reactants and stabilizes the intermediates. Additionally, the density of defects in Zn oxide is increased by the Cu-incorporation, resulting in improved deoxygenation step. Our findings may provide insightful understanding on the mechanism and guide the design of novel electrocatalyst for effective CO reduction.