Sulfonated block ionomers possess advantageous properties for a wide range of diverse applications such as desalination membranes, fuel cells, electroactive media, and photovoltaic devices. Unfortunately, their inherently high incompatibilities and glass transition temperatures effectively prevent the use of thermal annealing, routinely employed to refine the morphologies of nonionic block copolymers. An alternative approach is therefore required to promote morphological equilibration in block ionomers. The present study explores the morphological characteristics of midblock-sulfonated pentablock ionomers (SBIs) differing in their degree of sulfonation (DOS) and cast from solution followed by solvent-vapor annealing (SVA). Transmission electron microscopy confirms that films deposited from different solvent systems form nonequilibrium morphologies due to solvent-regulated self-assembly and drying. A series of SVA tests performed with solvents varying in polarity reveals that exposing cast films to tetrahydrofuran (THF) vapor for at least 2 h constitutes the most effective SVA protocol, yielding the anticipated equilibrium morphology. That is, three SBI grades subjected to THF-SVA self-assemble into well-ordered lamellae wherein the increase in DOS is accompanied by an increase in lamellar periodicity, as measured by small-angle X-ray scattering.