Membrane morphology plays a great role in determining the performance of polymer electrolyte membranes (PEMs), especially for direct methanol fuel cell (DMFC) applications. Membrane morphology can be divided into two types, which are dense and porous structures. Membrane fabrication methods have different configurations, including dense, thin and thick, layered, sandwiched and pore-filling membranes. All these types of membranes possess the same densely packed structural morphology, which limits the transportation of protons, even at a low methanol crossover. This paper summarizes our work on the development of PEMs with various structures and architecture that can affect the membrane�s performance, in terms of microstructures and morphologies, for potential applications in DMFCs. An understanding of the transport behavior of protons and methanol within the pores� limits could give some perspective in the delivery of new porous electrolyte membranes for DMFC applications. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.