Abstract: | This paper describes the peculiar co‐assembly supramolecular polymerization behavior of triphenylamine trisamide derivatives with d ‐alanine ( T‐ala ) or glycine ( T‐gly ) moieties. Concentration and temperature‐dependent circular dichroism (CD) spectroscopy revealed that the heating curves of co‐assemblies obtained at various molar ratios of T‐ala to T‐gly exhibited two distinct transition temperatures. The first transition was due to the transformation from coiled helical bundles to single helical fibers without handedness. The second was due to a change from typical elongation to nucleation. These phenomena were confirmed by solvent‐dependent decoiling of coiled helical structures and concentration‐dependent morphological analysis. The two transitioning temperatures were dependent on the concentration of T‐ala in the co‐assemblies, suggesting that T‐ala concentration plays an important role in the formation of coiled helical bundles. Our study demonstrated the first observation of two distinct transition temperatures in supramolecular polymers. |