Sulfonated polymers such as sulfonated polystyrene (sPS) and perfluorosulfonic acid (PSA) based materials have been of long-standing interest as sustainable solid acid catalyst alternatives to toxic homogeneous acid catalysts in the production of high-volume specialty chemicals. Our interest in these materials arises from the potential use of their uniquely heterogeneous hydrophobic-hydrophilic morphology for wearable chemical sensing in personal protective equipment (PPE). Sulfonated polymers can be applied as durable coatings on fiber blends using coaxial electrospinning to produce non-woven fabrics or onto polymeric Gore^® woven textiles. Prior research with these materials did not consider their catalytic properties and determined that water as liquid or vapor from sweat can actually promote chemical warfare (CW) agent transport. We demonstrate that the interface between dispersed hydrophilic clusters and the hydrophobic matrix of sulfonated polymers can be exploited to introduce catalytically active sites that trap and convert CW agents to a non-toxic organophosphate ester already used commercially as a flame retardant in clothing. Such trapping and conversion would not interfere with water transport and the associated color change provides a simultaneous means for optical detection. Despite significant understanding of how PSA polymer morphology impacts the transport behavior of ions, uncertainty remains over why some organic molecules become immobilized as they diffuse and react in this important class of materials while others do not. These aspects will be discussed in this presentation.