Dielectric relaxation behavior of SDS/β-CD self-organized with mass concentrations from 1% to 7% was investigated. The phase microstructure of SDS/β-CD aqueous solution was confirmed by analyzing the dielectric parameters. The dielectric relaxation behavior was attributed to the interfacial polarization between vesicle and medium, and the relaxation distribution parameter can indicate the shape transition from vesicles to microtubules with increasing concentration. Dielectric relaxation provided a new method to study surfactant organized self-assembly. Dielectric relaxation behavior of SDS / β-CD self-organized with mass concentrations from 1% to 7% was investigated. The phase microstructure of SDS / β-CD aqueous solution was confirmed by the dielectric parameters. The dielectric relaxation behavior was attributed to the interfacial polarization between vesicle and medium, and the relaxation distribution parameter can indicate the shape transition from vesicles to microtubules with increasing concentration. Dielectric relaxation provided a new method to study suggesting organized organized self-assembly.