Adsorption and aggregation behaviors of novel tetrasiloxane-tailed gemini surfactants N,N'-ditetrasiloxane-N,N'-digluconamide oligo ethylene glycol diglycidyl (Si-m-Si, where m is the number of ethylene glycol of 1, 2, and 3) were investigasted using surface tension, bromophenol blue encapsulation, dynamic light scattering (DLS), and transmission electron microscope (TEM) methods. The static surface tension of the aqueous Si-m-Si solutions measured at the critical aggregate concentration (CAC) was observed to be lower than that of traditional hydrocarbon gemini surfactants. This suggests that these newly synthesized gemini surfactants are capable of forming a closely packed monolayer film at the air/aqueous solution interface. With a combination of DLS data, TEM measurements, and bromophenol blue entrapment studies, formations of vesicles in Si-m-Si solutions appear to occur at a concentration well above the CAC. Moreover, the size of vesicles depended on their m values.