Phase diagrams are reported for glyme mixtures with simple lithium salts. The glymes studied include monoglyme (DME), diglyme, triglyme, and tetraglyme. The lithium salts include LiBETI, LiAsF6, LiI, LiClO4, LiBF4, LiCF3SO3, LiBr, LiNO3, and LiCF3CO2. The phase diagrams clearly illustrate how solvate formation and thermophysical properties are dictated by the ionic association strength of the salt (i.e., the properties of the anions) and chain length of the solvating molecules. This information provides critical predictive capabilities for solvate formation and ionic interactions common in organometallic reagents and battery electrolytes.