Semiempirical, ab initio, and density functional methods were used to determine the aggregation states of unsolvated and solvated N-lithioaziridine. Among the aggregated forms studied, the computational results suggest that in the absence of solvating ligands, N-lithioaziridine will exist primarily as a mixture of trimers and tetramers. The THF solvated lithioaziridines favored a tetrameric state whereas the HMPA and TMEDA solvated forms favored lower aggregation states.