The ternary Li-M-N-H systems, in which one of the Li sites in LiNH2 was substituted by transition metals (Ti, Cr, Fe, or Ni), were calculated with a first principle to explore new ternary systems for hydrogen storage. In order to evaluate their properties of hydrogen storage, the electronic structures, N-H chemical bonds, and thermodynamics of these systems were extensively computed and analyzed. In contrast to the Li-N-H system, these results proved a favorable energy cost to break the N-H bond and dissociate the H atom from these ternary amides. Of particular interest, there was a significant improvement in thermodynamics of the Li-Ti-N-H system, which had a reaction enthalpy of -46.6 kJ/mol compared with that of -75.67 kJ/mol in the Li-N-H system.