Abstract Cucurbituril (CB), a well‐known macrocyclic cavitand, has been used extensively to construct supramolecular aggregates. Based on host‐guest intertactions, an adamantanyl derivative guest molecule was designed and synthesized to prepare a supramolecular amphiphile with cucurbit[7]uril. In aqueous solution, the cucurbit[7]uril based supramolecular amphiphiles self‐assemble into well‐defined vesicles, and their disassembly can be achieved by addition of excess competitive agent 1‐adamantanamine hydrochloride. This vesicle functions as a new nanocapsule to encapsulate molecules within its hollow cavity. Through competitive disassembly of supramolecular amphiphiles, the vesicles behave as a novel drug delivery carrier.