Supramolecular assemblies are typically characterized by their dynamic nature due to the comparable weak non-covalent
interactions. While these properties confer adaptability, stability issues may limit application in areas such as drug delivery or
tissue engineering. Here, we show that supramolecular assemblies of amphiphilic polymers containing benzenetrispeptide and
benzenetrisureas motifs are inherently stable and non-dynamic at ambient conditions, but dynamic exchange can be selectively
activated. Stimulated emission depletion microscopy combined with automated image analysis revealed no dynamic exchange between
complementary labeled fibers independent of the length of the hydrophobic domains at ambient conditions in pure water for several
days. Competitive solvent addition facilitates dynamic exchange but compromises stability. Raising the temperature of the samples
in pure water to 60 °C, however, induces similar dynamics while fiber stability is maintained. The amphiphilic character in
combination with the strong hydrogen bonds seems to endow these supramolecular polymer brushes with unique switchable dynamics.