A new gemini surfactant with an azobenzene group incorporated in the spacer has been synthesized In. water, this new Compound forms a photo-responsive fluid, and the properties have been characterized by rheology and freeze-fracture electron microscopy (FF-TEM). UV/Vis irradiation causes a reversible change in zero shear viscosity of about 5 orders of magnitude. The different rheological properties correspond to different aggregation states in solution. A densely entangled network and small discrete micelles are respectively responsible for the high viscosity and the low viscosity state, as revealed by FF-TEM. The simplicity and high photo-efficiency of this single-component system act as a foundation for designing novel stimuli-responsive materials. (C) 2009 Elsevier Inc. All rights reserved.