We prepared a series of binary mixtures composed of selected Na salts and glymes (tetraglyme, G4, and pentaglyme, G5) with different salt concentrations and anionic species ([X](-): [N(SO2CF3)(2)](-) = [TFSA](-), [N(SO2F)(2)](-) = [FSA](-), ClO4-, PF6-) and studied the effects of concentration, anionic structure, and glyme chain length on their phase diagrams and solvate structures. The phase diagrams clearly illustrate that all the mixtures form 1:1 complexes, [Na(G4 or G5)(1)][X]. The thermal stability of the equimolar mixtures was drastically improved in comparison with those of diluted systems, indicating that all the glyme molecules coordinate to Na+ cations to form equimolar complexes. Single-crystal X-ray crystallography revealed that [Na(G5)(1)][X] forms characteristic solvate structures in the crystalline state irrespective of the paired anion species. A comparison of the solvate structures of the glyme-Na complexes with those of the glyme-Li complexes suggests that the ionic radii of the coordinated alkali-metal cations have substantial effects on the resulting solvate structures. The Raman bands of the complex cations were assigned by quantum chemical calculations. Concentration dependencies of cationic and anionic Raman spectra show good agreement with the corresponding phase diagrams. In addition, the Raman spectra of the 1:1 complexes strongly suggest that the glymes coordinate to Na+ cation in the same way in both liquid and crystalline states. However, the aggregated structure in the crystalline state is broken by melting, which is accompanied by a change in the anion coordination.