A phosphonium salt possessing three methacrylate groups has been incorporated into a photopolymeric system to generate highly cross-linked polyelectrolyte networks. Emergent chemical and physical Properties in the polymers were observed and attributed to the tandem increase in cross-link :density and ion-content upon incorporation of the self-cross-linking cation. Anion-exchange with bis(trifluoromethylsulfonyl)imide or dodecylbenzenesulfonate resulted in significant differences in wettability and ion-exchange behavior. The passivating effects of dodecylbenzenesulfonate were utilized to selectively pattern fluorescein dye into the polymer network, highlighting a new patterning procedure using ionic-bond forming reactions.