Two crystalline phases, (monoglyme)(2):LiClO4 and (diglyme)(2):LiClO4, have been isolated and characterized. The former consists of contact ion pairs in which the anions have bidentate coordination to the Li+ cations, while the latter consists of fully solvated Li+ cations in which the cations and anions do not directly interact. The two structures are useful as models for solvate structures in concentrated electrolyte mixtures. In particular, the phase behavior and solvate structures of solvent-salt mixtures are informative when coupled with vibrational spectroscopic analysis of ionic association behavior in solutions.