A detailed vibrational spectroscopic study of the ionic species present in the (PEO) x LiTf system (x = 3−100) indicates that “free” ions and ion pairs are the dominant species present in the dilute salt region at room temperature. When the salt concentration is increased to an O:M ratio of about 40:1, a band due to an aggregate species first appears and is assigned to the triflate ion vibrating in the (PEO)3LiCF3SO3 compound. The amorphous phase of (PEO)3LiCF3SO3 was studied by examining the temperature dependence of the spectra as the compound was heated through the melting transition at about 176 °C. Spectral behavior of the CH2 rocking modes and the COC stretching mode indicated that disordering above the melting temperature resulted in a broad distribution of −O−C−C−O− torsional angles. However the basic lithium-polyether backbone interaction was not been significantly changed for at least 15 °C above the transition temperature. Additional effects of thermal disordering were noted in the CF3 symmetric stretching mode and the antisymmetric stretching mode, reflecting an increase in the reorientational motion of CF3 end of the anion. These observations are consistent with the large values of the fluorine atom isotropic temperature factors noted in an X-ray diffraction study. Although the phase diagram reports only two phases present at room temperature (crystalline PEO and the compound (PEO)3LiCF3SO3), the spectral data clearly show that there is an additional phase present at intermediate salt concentrations which appears to be an amorphous PEO phase containing dissolved lithium triflate. If only crystalline PEO and the compound are present at equilibrium, the approach to the equilibrium state must be very slow indeed.