Crystalline phases of (triglyme)1:LiX (X = CF3SO 3-, BF4-, ClO4 -, and AsF6-) have been isolated and structurally characterized. The phases are isostructural and represent a novel form of Li+ cation coordination not observed in crystalline poly(ethylene oxide) (PEO)-salt phases. The crystal structure of a (triglyme)1:LiBPh4 phase has also been determined, which differs markedly from those found with the smaller anions. In addition, a more concentrated (triglyme)2/3:LiCF3SO3 phase has been characterized, which also displays a novel form of Li+ cation coordination. Such solvates represent models for interchain cation transport transition states in concentrated liquid and amorphous PEO electrolytes.