Ionic association in complexes of lithium trifluoromethanesulfonate with low-molecular-weight poly(ethylene oxide) dimethyl ethers was studied using Raman and infra-red vibrational spectroscopy. The relative concentrations of ion pairs and more highly associated ionic species are quite dependent on chain length. This dependence was measured in both the CF3 symmetric deformation mode and the SO3 symmetric stretching mode. The effect of the terminating group was considered by comparing the dimethyl ethers with hydroxy-terminated poly(ethylene oxide) at comparable chain lengths. Hydrogen bonding effects in the hydroxy-terminated poly(ethylene oxide) compounds were also found to depend on chain length.