Electrocatalytic nitrogen reduction reaction (NRR), as a green and sustainable method for ammonia synthesis, has become one of the candidates to substitute industrial Haber-Bosch ammonia synthesis in the near future. In this work, gold nanoparticles (Au NPs) were successfully anchored on bismuth sulfide nanorods (Bi2S3 NRs), which acted as highly efficient electrocatalytic NRR catalysts. The N-philic nature of Bi and the unique mutual coordination of Au-S-Bi can greatly promote the nitrogen adsorption and form the intermediate product N2H*, achieving a boosted improvement in the NRR activity through a continuous hydrogenation reaction. Definitely, the as-synthesized Au(111)@Bi2S3 nanorod catalyst exhibits an excellent NH3 generation rate of 45.57 μg h-1 mgcat.-1 with a faradic efficiency of 3.10% at -0.8 V vs reversible hydrogen electrode. High stability and reproducibility are also demonstrated throughout the electrocatalytic NRR process. Density functional theory calculations were performed to further understand the NRR catalytic mechanism on the Au(111)@Bi2S3 nanorods catalyst.