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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.