One of the key components to determine polymer electrolyte membrane fuel cell (PEMFC) performances is a polymer electrolyte membrane (PEM), the representative PEM material is perfluorinated sulfonic acid (PFSA) ionomers. PFSA ionomers such as Nafion®and 3M® ionomers have been widely used as PEM materials for fuel cells owing to their excellent chemical inertness and high proton conductivity. Generally, polymeric materials are highly influenced by the membrane fabrication histories including casting solvents, thermal annealing temperature and time, when they are converted in the membrane forming process. In this study, 3M PFSA ionomer membranes were systematically prepared under different fabrication histories. Their morphological contribution on fundamental characteristics, transport behavior, and electrochemical performances were disclosed.