AbstractAmmonia, a pivotal chemical feedstock and a potential hydrogen energy carrier, demands efficient synthesis as a key step in its utilization. The traditional Haber‐Bosch process, known for its high energy consumption, has spurred researchers to seek ammonia synthesis under milder conditions. Advances in surface science and characterization technologies have deepened our understanding of the microscopic reaction mechanisms of ammonia synthesis. This article concentrates on gas‐solid phase ammonia synthesis, initially exploring the latest breakthroughs and improvements in thermal catalytic synthesis. Building on this, it especially focuses on emerging external field‐driven alternatives, such as photocatalysis, photothermal catalysis, and low‐temperature plasma catalysis strategies. The paper concludes by discussing the future prospects and objectives of nitrogen fixation technologies. This comprehensive review is intended to provide profound insights for overcoming the inherent thermodynamic and kinetic constraints in traditional ammonia synthesis, thereby fostering a shift towards “green ammonia” production and significantly reducing the energy footprint.