In this communication, we show that ultrathin Au nanowires (NWs) with dominant edge sites on their surface are active and selective for electrochemical reduction of CO2 to CO. We first develop a facile seed-mediated growth method to synthesize these ultrathin (2 nm wide) Au NWs in high yield (95%) by reducing HAuCl4 in the presence of 2 nm Au nanoparticles (NPs). These NWs catalyze CO2 reduction to CO in aqueous 0.5 M KHCO3 at an onset potential of -0.2 V (vs reversible hydrogen electrode). At -0.35 V, the reduction Faradaic efficiency (FE) reaches 94% (mass activity 1.84 A/g Au) and stays at this level for 6 h without any noticeable activity change. Density functional theory (DFT) calculations suggest that the excellent catalytic performance of these Au NWs is attributed both to their high mass density of reactive edge sites (≥16%) and to the weak CO binding on these sites. These ultrathin Au NWs are the most efficient nanocatalyst ever reported for electrochemical reduction of CO2 to CO.