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The cloudy Silwet L-77 aqueous solution on the concentration range from 0.5% to 50% was investigated by dielectric relaxation spectroscopy. The concentration dependence of phase microstructure was confirmed by means of analyzing the dielectric parameters of bulk solution. The relaxation behavior was assigned to the interfacial polarization between the micelle and the medium, and the relaxation distribution parameter was used to figure the shape transition from sphere to ellipsoid with the concentration increasing. The synchronous reduction of permittivity and conductivity indicated the formation of the lamellar phase. As compensation, the quantity of the surfactant liquid phase gradually decreased, whose shape constantly kept ellipsoidal.