The photoelectrochemical reduction of nitrogen to ammonia (NH3) is a sustainable and cost-effective process. The photoelectrocatalysts adsorb light, activate N2, and transport electrons efficiently to achieve high-yield NH3. In the present work, gold-tungsten sulfide-anchored reduced graphene oxides (Au-WS2@RGO) are developed as highly efficient photoelectrocatalysts for the N2 reduction reaction (NRR) to synthesize NH3. The effect of Au nanoparticles loaded on WS2@RGO is optimized to achieve hierarchical 2D Au-WS2@RGO with excellent electrical conductivity, large active surface area, and unique porous network. Photoelectrocatalytic NRR of Au-WS2@RGO achieves remarkable NH3 production rates with ultrahigh NH3 yield of 34 mu gh-1mgcat-1 at-0.6 V, tremendous faradaic efficiency (FE) of 16.2 %, long durability for about 14 h, and prolonged lifetime of photo -carriers. DFT calculations support the experimental findings and demonstrate that Au-WS2@RGO as an effeient NRR catalyst with low overpotential. The Au-WS2@RGO shows the highest NRR performances even in atmo-spheric air (AirRR) and outperforms the state-of-the-art NRR catalysts. The high AirRR performance and dura-bility of Au-WS2@RGO make it a promising alternative to Au-based NRR catalysts in photo electrolyzers. Further, an innovative methodology will be proposed for high-efficiency urea fertilizer production using Au-WS2@RGO-based NRR photocatalysts.