The polymer electrolyte systems of Sn(CF3SO3)(2) and Pb(CF3SO3)(2) dissolved in poly(propylene oxide) triol of average molecular weight 3000 were studied using Raman and infrared vibrational spectroscopy. The salt concentrations were varied between 20 and 120 ether oxygens per cation. The nu(s)(SO3) bands from cation coordinated triflate ions for both tin and lead solutions are shifted toward lower frequencies relative to the "free" anion, in startling contrast to the shifts to higher frequencies observed in monovalent triflate PPO Systems. The splitting of the corresponding cation-coordinated nu(as)(SO3) bands was measured. Temperature-dependence studies were performed from room temperature to 100 degrees C. The effect of the OH end group was investigated by alkylating the PPO, i.e., exchanging the hydrogen of the OH groups for CH3, and comparing the respective Raman and infrared spectra. The relative concentrations of the different ionic species change considerably for the OCH3-capped PPO; this can be attributed to the removal of hydrogen bonding between the SO3 end of the triflate anion and the OH group on the polymer molecule. A model study was also performed for tin triflate and lead triflate dissolved in acetonitrile at concentrations ranging from 0.05 to 0.3 m.