Perfluorinated sulfonic acid (PFSA) ionomers such as Nafion® and 3M ionomers have been used as polymer electrolyte membrane materials for fuel cells owing to their excellent chemical inertness, and high proton conductivity. The membrane characteristics are highly affected by their fabrication history as well as chemical structure. It is important to choose appropriate solvents for membrane preparation, since a relatively low solubility of PFSA ionomers may result in fairly different morphological features, which influence the transport behavior of small molecules such as proton and water through the resulting membranes. In this study, PFSA membranes are prepared using a variety of solvents with different properties and their fundamental characteristics and morphologies are compared each other.