Conformational changes in diethylene glycol dimethyl ether (diglyme) and high molecular weight poly(ethylene oxide) induced by complexation with Lithium trifluoromethanesulfonate (LiCF3SO3) have been investigated using Raman scattering and infrared transmission spectroscopy. In both the diglyme and polymer complex new bands were observed in spectral regions involving a significant amount of CH2 bending motion. These bands are attributed to a conformation which is not energetically favored in the pure polymer or oligomer but which is stabilized through interactions of the cation with the polyether oxygen atoms. The structure of the new conformer is discussed.