Sulfonated aromatic hydrocarbon-based ionomers are potential constituents of next-generation polymer electrolyte fuel cells (PEFCs). Widespread application is currently limited due to their susceptibility to radical-initiated oxidative degradation that, among other intermediates, involves the formation of highly reactive aromatic cation radicals. The intermediates undergo chain cleavage (dealkylation/dearylation) and the loss of protogenic sulfonate groups, all leading to performance loss and eventual membrane failure. Laser flash photolysis experiments indicated that cation radicals can also be formed via direct electron ejection. We aim to establish the major degradation pathway of proton-exchange membranes (PEMs). To this end, we irradiated aqueous solutions of phenyl sulfonate-type model compounds with a Xe arc lamp, thus generating radicals. The radicals were trapped by 5,5-dimethyl-1-pyrroline N-oxide (DMPO), and the formed adducts were observed by electron paramagnetic resonance (EPR). The formed DMPO spin adducts were assigned and relative adduct concentrations were quantified by simulation of the experimental EPR spectra. Through the formation of the DMPO/^•SO₃^- adduct, we established that desulfonation dominates for monoaromatic phenyl sulfonates. We observed that diaryl ether sulfonates readily undergo homolytic C-O scission that produces DMPO/^•aryl adducts. Our results support the notion that polyphenylene sulfonates are the most stable against oxidative attack and effectively transfer electrons from DMPO, forming DMPO/^•OH. Our findings help to identify durable moieties that can be used as building blocks in the development of next-generation PEMs.