The electrocatalytic nitrogen to ammonia has attracted intensive attention but suffers from severe bottlenecks of low Faradaic efficiency and NH3 yield. Herein, we report a two-step process to prepare amorphous sulfur multilayer decorated gold nanowires (S/Au NWs) as superior catalysts for electrochemical NH3 production. The chemisorbed sulfur multilayers are favorable for selective hydrogenation of nitrogen to ammonia and provide sufficient exposed active sites for nitrogen reduction reaction (NRR). The S/Au NWs show a high NH3 yield of 21.04 μg h–1 mg–1cat. and Faradaic efficiency of 15.34%, as well as excellent durability. The superior NRR performance of Au catalysts with S chemisorption would stimulate interest toward NRR catalyst design of sulfur bonding to metal surfaces.