Solutions of lithium hexafluroantimonate, LiSbF6, dissolved in diethylene glycol dimethyl ether (diglyme), CH3O(CH2CH2O)(2)CH3, are used as a model for high molecular weight poly(ethylene oxide), PEO, complexed with LiSbF6. During this work, a 2:1 diglyme:LiSbF6 crystal was discovered and its structure solved by single-crystal X-ray diffraction techniques. The compound crystallizes in the orthorhombic Pccn space group with Z = 4. In this crystal, the lithium ion is 6-fold coordinated by two diglyme molecules, while the anions are isolated. Raman and FTIR vibrational spectroscopy were used to study both the crystal and a series of diglyme-LiSbF6 solutions. Similarities in modes sensitive to molecular conformation show that the local conformational structure in the crystal also occurs in diglyme-LiSbF6 solutions.