Spontaneous formation of supramolecular vesicles which are triggered by the formation of [4]pseudorotaxane B was demonstrated, whereas both Guest and [2]pseudorotaxane A, the precursors of [4]pseudorotaxane B, only assemble into micelles in DMF/water solution. The remarkable transformation of Guest from micelles to supramolecular vesicles was confirmed through DLS, TEM, and Cryo-TEM experiments. The cumulative release of a model drug, 5-carboxyfluorescein (CF), was used to determine the permeability of the supramolecular vesicles. No leakage of entrapped CF was observed within 48 h by fluorescence measurement, indicating the high stability of supramolecular vesicles. The formation mechanism of supramolecular vesicles self-assembled by [4]pseudorotaxane B was also discussed. In [4]pseudorotaxane B, CB[6] is used to increase the hydrophobic property of site beta, which acts as hydrophobic "tail." Meanwhile, CB[7] plays the role of increasing "head area" of site alpha, which acts as hydrophilic "head." The synergistic effect of CB[6] and CB[7] induces the formation of supramolecular vesicles. Moreover, the effect of DMF content was investigated by TEM observations. It was found that the [4]pseudorotaxane B can self-assemble into regular supramolecular vesicles when the DMF content is in the range of 50-70%. (C) 2013 Elsevier Inc. All rights reserved.