Electronic structure and the vibrational frequencies of CH3(OCH2CH2)(n)OCH3-M+-CF3SO3- (n) 2-4, M) Li, Na, and K) complexes have been derived from ab initio Hartree-Fock calculations. The metal ion shows varying coordination from 5 to 7 in these complexes. In tetraglyme-lithium triflate, Li+ binds to one of the oxygens of CF3SO3-( triflate or Tf-) unlike for potassium or sodium ions, which possess bidentate coordination. Structures of glyme-MTf complexes thus derived agree well with those determined from X-ray diffraction experiments. The metal ion binds more strongly to ether oxygens of tetraglyme than its di- or triglyme analogues and engenders contraction of SO ( for oxygens binding to metal ion) bonds with consequent frequency upshift for the corresponding vibration in the complex relative to those in the free MTf ion pairs. Complexation of the diglyme with LiTf engenders the largest downshift ( 91 cm(-1)) for the SO2 stretching vibration of the free anion, which suggests stronger binding of lithium to the diglyme than the tri- ( 79 cm(-1)) or tetraglyme ( 70 cm(-1)). A frequency shift in the opposite direction for the SO ( where oxygens do not coordinate to the metal) and CF3 stretchings, which stems from the ion-polymer and anion-ion interactions, has been noticed. These frequency shifts have been analyzed using natural bond orbital analysis and difference electron density maps coupled with molecular electron density topography.