Molecular design, features that, endow amphiphilic supramolecular assemblies with a unique temperature-sensitive transition have been investigated. We find that conformational rigidity in the backbone IS an important feature for eliciting this feature. We also find that intramolecular hydrogen-bonding can in-duce such rigidity in amphiphile backbone. Guest encapsulation stability of these assemblies was found to be significantly altered Within, a narrow temperature window, which correlates with the temperature-sensitive size transition of the molecular assembly. Molecular design principles demonstrated here,could have broad implications in developing future temperature-responsive systems.