A linear-hyperbranched supramolecular amphiphile was synthesized through the noncovalent coupling of adamantane-functionalized long alkyl chain (AD-CIV n = 12, 18, 30) and hyperbranched polyglycerol grafted from beta-cyclodextrin (CD-g-HPG) by the specific AD/CD host guest interactions. The obtained supramolecular C-n-b-HPGs self-assembled into unilamellar vesicles with great ductility that could be disassembled readily under a competitive host of beta-CD.