Three novel amphiphilic dicephalic (double-headed) surfactants containing oligo(ethylene-oxide)methyl-ether and a sugar moiety TGA-m (m = 1, 2, and 3) that incorporate a tetrasiloxane at the terminus of a hydrocarbon chain were designed and synthesized. Their surface activity and aggregation behavior in aqueous solution were systematically investigated by surface tension, dynamic light scattering (DLS), and transmission electron microscopy (TEM) techniques at 298 K. The surface tension measurements provided the critical aggregation concentration (CAC) and the surface tension at the CAC (γ(cac)). In addition, with application of the Gibbs adsorption isotherm, the maximum surface excess concentration (Γ(max)) and the minimum surface area/molecule (A(min)) at the air-water interface were estimated. The effect of EO chain length on the surface activity and aggregation behavior was also investigated. It was found that both the γ(cac) and the CAC were lower than those for reported traditional hydrocarbon surfactants. Aggregates of three surfactants, TGA-m (m = 1, 2, and 3), formed in aqueous solutions could be assigned as spherical vesicles as suggested by analysis using DLS and TEM. Moreover the formation of vesicles can be confirmed by the encapsulation of bromophenol blue. These results indicate that these three surfactants have excellent efficiencies of vesicle formation and surface tension reduction in the aqueous phase.