Lithium alloys are synthesized by reactions between lithium metal and group 14 elements, such as carbon, silicon, germanium, and tin. The nitrogenation and denitrogenation properties are investigated by thermal and structural analyses. All alloys dissociate the nitrogen triple bond of gaseous molecules to form atomic state as nitrides below 500 °C, which is lower than those required for conventional thermochemical and catalytic processes on nitride syntheses. For all alloys except for germanium, it is indicated that nanosized lithium nitride is formed as the product. The denitrogenation (nitrogen desorption) reaction by lithium nitride and metals, which is an ideal opposite reaction of nitrogenation, occurs by heating up to 600 °C to form lithium alloys. Among them, the lithium-tin alloy is a potential material to control the dissociation and recombination of nitrogen below 500 °C by the reversible reaction with the largest amount of utilizable lithium in the alloy phase. The nitrogenation and denitrogenation reactions of the lithium alloys at lower temperature are realized by the high reactivity with nitrogen and mobility of lithium. The above reactions based on lithium alloys are adapted to the ammonia synthesis. As a result, ammonia can be synthesized below 500 °C under 0.5 MPa of pressure. Therefore, the reaction using lithium alloys is recognized as a pseudocatalyst for the ammonia synthesis.