In order to improve the stability of polymeric vesicles, supramolecular vesicles are developed via self-assembly of the inclusion of gamma-cyclodextrin (gamma-CD) and 1-pyrenemethyl palmitate (Py-pal). The inclusion has one hydrophilic head and double hydrophobic tails, which looks like the phospholipid. From the transmission electron microscopy (TEM) image, it can be observed that the average diameter of supramolecular vesicles is approximately 55 nm and there is a huge cavity in supramolecular vesicles. Due to the photo-breakable ester of Py-pal, supramolecular vesicles are broken under UV irradiation. Supramolecular vesicles are used as UV-responsive drug carriers to release the hydrophilic drug such as doxorubicin hydrochloride (DOX center dot HCl).