Six novel siloxane-based surface-active ionic liquids (SAILs)-siloxane ammonium carboxylate [Si(n)N(2)-CA(1), (n = 3, 4)]-were designed and synthesized. Their melting points, surface activities, and self-aggregation behavior in aqueous solution were studied. The results showed that because of the bulky hydrophobic siloxane chains at the end of the tail, all six siloxane-based SAILs are room-temperature ionic liquids (RT-SAILs). The introduction of the siloxane group can reduce the melting point of ionic liquids to below room temperature and can promote the micellization and aggregation behavior more efficiently. These siloxane-based SAILs can greatly reduce the surface tension of water, as shown by the critical aggregation concentration (gamma(CAC)) values of 20 mN.m(-1); all six siloxane RT-SAILs can form a vesicle spontaneously in aqueous solution, indicating potential uses as model systems for biomembranes and vehicles for drug delivery.