Various analytical techniques (FTIR, ESR, SAXS, and dynamic mechanical analysis) were used to study the effect of low molecular weight solvents (diluents) on structure and properties of sulfonated polystyrene ionomers. The results were interpreted in terms of a two phase morphology for the ionomer where polar solvents interact most strongly with the ionic-rich phase and non-polar solvents with the ion-poor phase. Spectroscopic evidence is presented that demonstrates the relative ability of different solvents to perturb the local ionic interactions that are prevalent in these materials.