ac impedance, Raman spectroscopy and pulsed field gradient NMR measurements have been conducted on solutions of poly(ethylene oxide), dimethyl ether of molecular weight 400 complexed, with LiCF3SO3 as a function of salt concentration; the ether oxygen to alkali metal cation ratios (O:M) ranging from 53:1 to 563:1. From an analysis of the nu(s)(SO3) band envelope of the triflate anion, the relative concentrations of anions in various chemical environments have been calculated. A slight redissociation effect is observed with increasing salt concentration which correlates well with an observed increase in the molar conductivity. Pulsed field gradient NMR measurements show that the H-1, Li-7 and F-19 self-diffusion coefficients all decrease monotonically with increasing salt concentration. Experimental conductivity data is compared to values calculated from the diffusion coefficients using the Nernst-Einstein relation. We find that the calculated values are higher for all concentrations; the discrepancy increases with decreasing salt concentration.