Ionomer composition and morphology impacts functional group distribution, water and ion-transport, and physical properties related to toughness, and degradation resistance. NEXAR MD9100 a pentablock copolymer (PBC) film morphology was dramatically altered when solution-cast into a film using tetrahydrofuran (THF) versus a cyclohexane: heptane (C:H) mixture. Film property and morphology changes were evaluated using Transmission Electron Microscopy (TEM), Small-Angle X-ray Scattering (SAXS), and electrochemical impedance spectroscopy. These changes were compared to Nafion 117 and Nafion 212. Average sulfonated inter-domain spacing through the film's thickness increased from 22.3nm (C:H cast) to 30.5nm (THF cast) that was estimated using SAXS. TEM revealed that PBC solution-cast films from C:H contained a random distribution of discrete sulfonated domains. An ordered PBC morphology consisting of lamella and hexagonally packed ion groups were created from a THF solution-cast film. These changes were attributed to favorable solvent-ionomer interactions during solvent evaporation and film densification. This ordered morphology led to increased conductivity (4.5mS/cm versus 47.8mS/cm), improved fuel cell power (19mW/cm2 versus 160mW/cm2), enhanced ionomer actuation (3.0cm versus 6.9cm), and modest self-discharge improvements for a vanadium redox-flow battery. This study demonstrates that morphology impacts ionomer physical properties, transport, and device function.