The surface structure and dewetting process of thin films of complex perfluorinated ion-containing polymers have been studied with atomic force microscopy. These polymers, or ionomers, consist of hydrophilic, hydrophobic, and ionic groups, which are noncompatible with one another, and this results in the association of the polymers into supramolecular structures. These types of polymers have a broad range of technological uses, ranging from thin selective coatings to fuel cells in the form of polymer electrolyte membranes. As the technology calls for thinner films, the interfacial structure and dynamics (wetting/dewetting) of the films become critical in controlling the overall behavior of the polymers. The ionomer under consideration forms structured films consisting of bundles of micelles. These ultrathin films do not dewet above the glass-transition temperatures of the polymers, contrary to what has been observed in thin diblock copolymers. Perturbing the system with a high-ionic-strength solution, however, results in a breakup of the primary aggregate and enhances the adhesion of the films and their stability.