The advancement of cost-effective and selective electrocatalyst towards CO₂ to CO conversion is crucial for renewable energy conversion and storage, thus to achieve carbon-neutral cycle in a sustainable manner. In this communication, we report that Cu₂Sb decorated Cu nanowire arrays on Cu foil act as a highly active and selective electrocatalyst for CO₂ to CO conversion. In CO₂-saturated 0.1 M KHCO₃, it achieves a high Faraday efficiency (FE) of 86.5% for CO, at -0.90 V vs. reversible hydrogen electrode (RHE). The H₂/CO ratio is tunable from 0.08:1 to 5.9:1 by adjusting the potential. It is worth noting that HCOO^- product was totally suppressed on such catalyst, compared with Sb counterpart. The improving selectivity for CO could be attributed to the bimetallic effect and nanowire arrays structure.