Four carbohydrate-modified siloxane surfactants. Si(n)N-GA and Si(n)N-LA (n = 3, 4), were designed and synthesized. Their surface activities, adsorption, and aggregation behavior in aqueous solution were investigated by surface tension measurements, dynamic light scattering (DLS) and transmission electron microscopy (TEM). Due to the bulky siloxane moiety at the end of hydrophobic chains, the surfactant solutions displayed low critical aggregation concentration (cac) and low surface tension. Surface tension measurement for all three surfactants are under 22 mN . m(-1), much lower than those of ordinary hydrocarbon surfactants. Due to its poor solubility in water, surface tension of Si(4)N-GA could not be measured. DLS and TEM analysis of Si(3)N-GA, Si(3)N-LA, and Si(4)N-LA aqueous solutions revealed self-assembled spherical vesicles, indicating potential applications as microsphere drug delivery systems and as models of biomembranes.