Most alternate membrane materials for fuel cells have in the past relied upon a post-sulfonation process to generate ionic groups capable of transporting protons from the anode to the cathode. These random post sulfonations showed some promise, but in general they produced materials that were not sufficiently stable or protonically conductive at ion exchange capacities where aqueous swelling could be restricted. In response, our group began to synthesize disulfonated monomers that could be used to incorporate into random copolymer proton exchange membranes. The expected limitation was that the aromatic polymers might not be stable enough to withstand fuel cell conditions. However, this was mostly based upon an accelerated test (Fenton's Reagent Test), which did not seem to be a reliable predictor of performance. A better approach has been to evaluate the open circuit voltage (OCV) for alternate membranes, as well as the benchmark perfluorosulfonic acid systems. When this is done, the aromatic ionomers of this study, primarily based upon disulfonated polyarylene ether sulfones, show up quite well. Real time 3000 hours DMFC results have also been generated. Obtaining conductive materials at low humidities is another major issue where alternate membranes have not been particularly successful. In order to address this problem, multiblock copolymers with relatively high water diffusion coefficients have been designed, which show promise for conductivity at lowered humidity. An overview of these systems will be discussed in this lecture.