Two end-decorated homopolymers, poly(styrene)-beta-cyclodextrin (PS-beta-CD) and poly(ethylene oxide)-ferrocene (PEO-Fc), can orthogonally self-assemble into a supramolecular diblock copolymer (PS-beta-CD/PEO-Fc) in aqueous solutions based on the terminal host-guest interactions. These assemblies can further form supramolecular vesicles, and their assembly and disassembly behaviors can be reversibly switched by voltage through the reversible association and disassociation of the middle supramolecular connection. The vesicles possess an unprecedented property that their assembly or disassembly speed can be controlled by the applied voltage strength. Luminescence spectroscopy demonstrates that the vesicles act as nanocapsules carrying molecules within their hollow cavities and that the external voltage strength accurately regulates the drug release time.