The stabilization energies (ΔEform) calculated for the formation of the Li+ complexes with mono-, di- tri- and tetra-glyme (G1, G2, G3 and G4) at the MP2/6-311G** level were −61.0, −79.5, −95.6 and −107.7 kcal mol−1, respectively. The electrostatic and induction interactions are the major sources of the attraction in the complexes. Although the ΔEform increases by the increase of the number of the O⋅⋅⋅Li contact, the ΔEform per oxygen atom decreases. The negative charge on the oxygen atom that has contact with the Li+ weakens the attractive electrostatic and induction interactions of other oxygen atoms with the Li+. The binding energies calculated for the [Li(glyme)]+ complexes with TFSA− anion (glyme=G1, G2, G3, and G4) were −106.5, −93.7, −82.8, and −70.0 kcal mol−1, respectively. The binding energies for the complexes are significantly smaller than that for the Li+ with the TFSA− anion. The binding energy decreases by the increase of the glyme chain length. The weak attraction between the [Li(glyme)]+ complex (glyme=G3 and G4) and TFSA− anion is one of the causes of the fast diffusion of the [Li(glyme)]+ complex in the mixture of the glyme and the Li salt in spite of the large size of the [Li(glyme)]+ complex. The HOMO energy level of glyme in the [Li(glyme)]+ complex is significantly lower than that of isolated glyme, which shows that the interaction of the Li+ with the oxygen atoms of glyme increases the oxidative stability of the glyme.