Abstract Vesicles form spontaneously in aqueous solution of a novel sugar-based surfactant containing trisiloxane [Si(3)N-GHA]. The transition was monitored among the monomer, micelle and vesicle through the variation of surface tension, accompanied by surface tension measurements. The vesicles of a trisiloxane containing sugar-based surfactant have been characterized by dynamic light scattering (DLS) and negative-stained transmission electron microscopy (TEM). The vesicle aggregation can be explained by the critical packing parameter derived from an analysis of chemical structure.