This work discusses the effect of isopropyl phosphate (IP) on the transport properties of sulfonated poly(styrene‐isobutylene‐styrene) (SO3H SIBS) as membranes for direct methanol fuel cell (DMFC) and chemical and biological protective clothing (CBPC) applications. The properties were determined as a function of SIBS sulfonation level (i.e., 24, 34, 49, and 84 mol %) and IP loading (i.e., 1, 3, 5, 11, and 15 wt %). A comprehensive material characterization study (e.g., FTIR, TGA, AFM, and SAXS) was performed to confirm the presence of the phosphate groups in the polymer matrix, assess the thermal stability of the proton‐exchange membranes (PEMs), and understand how the unique interactions between the phosphate and sulfonic groups influenced the nanostructure of SO3H SIBS. The transport properties, water absorption capabilities (i.e., swelling ratio, water uptake, etc.), oxidative stability, and ion‐exchange capacity (IEC) were performed to evaluate the impact of IP on the properties of the resulting solvent‐casted membranes. Results suggest that the morphology, thermal stability, and vapor permeability are governed by the sulfonation level, whereas the IEC, oxidative stability, water absorption capabilities, and the rest of the transport properties are dominated by the ionic content (i.e., sulfonic and phosphate groups) and their synergistic effects.