The development of a selective and efficient catalyst for CO2 electroreduction is a great challenge in CO2 storage and conversion research. Silver metal is an attractive alternative due to its enhanced catalytic performance of CO2 electroreduction to CO. Here, we prepared Ag nanowires anchored on carbon support as an excellent electrocatalyst with remarkably high selectivity for the CO2 reduction to CO. The CO Faradic efficiency was approximately 100%. The enhanced catalytic performances may be ascribed to dense active sites exposed on the Ag nanowires’ high specific surface area, by the uniform dispersion of Ag nanowires on the carbon support. Our research demonstrates that Ag nanowires supported on carbon have potential as promising catalysts in CO2 electroreduction.