An aqueous vesicular system that is switchable by electric potential without addition of any chemical redox agents into the solution is demonstrated using redox-responsive self-assembly of an amphiphilic rod-coil molecule consisting of a tetraaniline and a poly(ethylene glycol) block. The vesicle membrane is split by an oxidizing voltage into smaller pucklike micelles that can reassemble to form vesicles upon exposure to a reducing voltage. The switching mechanism is explained by the packing behavior of the tetraaniline units constituting the membrane core, which depends on their oxidation states.