Reversible reaction involving Li amide (LiNH2) and Li imide (Li2NH) is a potential mechanism for hydrogen storage. Recent synchrotron x-ray diffraction experiments [W. I. David et al., J. Am. Chem. Soc. 129, 1594] suggest that the transformation between LiNH2 and Li2NH is a bulk reaction that occurs through non-stoichiometric processes and involves the migration of Li + and H + ions. In order to understand the atomistic mechanisms behind these processes, we carry out comprehensive first-principles studies of native point defects and defect complexes in the two compounds. We find that both LiNH2 and Li2NH are prone to Frenkel disorder on the Li sublattice. Lithium interstitials and vacancies have low formation energies and are highly mobile, and therefore play an important role in mass transport and ionic conduction. Hydrogen interstitials and vacancies, on the other hand, are responsible for forming and breaking N−H bonds, which is essential in the Li amide/imide reaction. Based on the structure, energetics, and migration of hydrogen-, lithium-, and nitrogen-related defects, we propose that LiNH2 decomposes into Li2NH and NH3 according to two competing mechanisms with different activation energies: one mechanism involves the formation of native defects in the interior of the material, the other at the surface. As a result, the prevailing mechanism and hence the effective activation energy for decomposition depend on the surface-tovolume ratio or the specific surface area, which changes with particle size during ball milling. These mechanisms also provide an explanation for the dehydrogenation of LiNH2+LiH mixtures.