A comparative vibrational spectroscopic study of 2-methoxyethyl ether solutions containing dissolved LiCF3SO3 and NaCF3SO3 is reported. The strong, infrared active metal oxygen stretching mode was observed as a broad band at 400 cm-1 in the LiCF3SO3 solution and at 180 cm-1 in the NaCF3SO3 solution. Several low-frequency modes originating in intramolecular CF3SO 3 - motions are reported and assigned. The relative concentrations of the various ionic species present are described as a function of salt concentration in both systems. Finally, changes in the local conformation of the 2-methoxyethyl ether backbone due to interactions of the ether oxygens with the cations are discussed.