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Mechanocatalytic ammonia synthesis is a novel approach toward ammonia synthesis under mild conditions. However, many open questions remain about the mechanism of mechanocatalytic ammonia synthesis, as well as the structure of the active catalysts during milling. Herein, the structural evolution of an in situ synthesized titanium nitride catalyst is explored during extended milling. The yield of ammonia bound to the catalyst surface was found to strongly correlate with an increase in catalyst surface area during milling, although a lower surface concentration of ammonia at earlier milling times suggests a delay in ammonia formation, corresponding to the conversion of the titanium metal pre-catalyst into the nitride. Small pores develop in the catalyst during milling due to interstitial spaces between agglomerated titanium nitride nanoparticles, as shown by SEM and TEM. In the first 6 h, the titanium is both converted to a nitride and fractured to smaller particles, before an equilibrium state is reached. After 18 h of milling, the catalyst nanoparticles appear to crystallize into a denser material, resulting in a loss of surface area and pore volume.