A systematic study of the ternary complex formation process for aromatic amino acids using ucurbituril (CB) and a viologen amphiphile shows that the affinity of the amino acid needs to be higher or in a comparable range to that of CB for the amphiphile in order to form the ternary complex. Based on these observations, a supramolecular peptide amphiphile and its corresponding vesicle are prepared using a peptide containing an azobenzene moiety. The azobenzene group at the N-terminus of the peptide served as the second guest for CB. The vesicles obtained from this peptide amphiphile show response to a number of external triggers. The trans-cis isomerization of the azobenzene group upon irradiation with UV-light of 365 nm leads to the breakdown of the ternary complex and eventually to the disruption of the vesicle. The deformation-reformation of the vesicle can be controlled by illuminating the disrupted solution with light of 420 nm as it facilitates the cis-trans isomerization. Thus, the vesicle showed a controlled and reversible response to UV-light with the ability for manipulation of the formation-deformation of the vesicle by the choice of an appropriate wavelength. The vesicle showed response to a stronger guest (1-adamantylamine) for CB, which displaces both the guests from the CB cavity and consequently ruptures the vesicle structure. 2,6-Dihydroxynaphthalene acts as a competitive guest and thereby behaves as another external trigger for replacing the peptide from the CB cavity by self-inclusion to form the ternary complex. Henceforth, it allows retaining the vesicle structure and results in the release of the peptide from the vesicle.