Recovery of H-2 and N-2 from the tail gases of the ammonia synthesis plant could significantly improve the ammonia output and economic benefits. In this work, we measured the formation conditions of tail gas hydrates, conducted separation of tail gases via hydrate formation in tetrahydrofuran (THF) and ammonia solution, and proposed a two-stage separation process. The separation effects of temperature, pressure, and gas-liquid ratio (GLR) were investigated as well. The results show that the two-stage separation can effectively remove CH4 from the tail gases. The total concentration of H-2 and N-2 in gas products is more than 94 mol %, with a recovery of up to 95%.