Amphiphilic molecules can form into different structures, such as micelle, microemulsion, vesicle, liposome, liquid crystals, and so on by self-associating. The Dielectric Spectroscopy (DS) method has been applied to the systems of micelle and microemulsion successfully. For the first time the author put the method to the system of vesicle of CTAB/SDBS. The experiments show clear dielectric relaxation and the results were discussed primarily. The Dielectric Spectroscopy (DS) method has been applied to the systems of micelle and microemulsion successfully. For the first time the author put the method to the system of vesicle of CTAB / SDBS. The experiments show clear dielectric relaxation and the results were looked primarily.