The lithium ion is an important type of electrolyte that has technological applications in the manufacture of lithium ion cells, therefore, a better understanding of the nature of Its solutions is desirable. When associated to the radical anion of biphenyl in an organic solvent, it forms conducting solutions comparable to strong electrolytes such as lithium perchlorate. We have studied the lithium biphenyl solution in dimethoxyethane using DFT calculations. The nature of these ionic. solutions is described in terms of a dynamic equilibrium between different types of ionic associations, the composition of which depends on the solvent and the temperature. The X-ray structure of [Li(+)center dot 4C(5)H(10)O][C(12)H(10)(center dot-)], a solvent-separated ion pair of lithium biphenyl complexed with tetrahydropyran, is reported. Its main structural characteristics coincide with the calculated one, which we think is the dominant species at room temperature, in agreement with the available physicochemical data.