An amphiphilic phosphodiester-linked azobenzene trimer has been exploited in the development of stimuliresponsive,w ater-soluble supramolecular polymers.T he trimer can reversibly undergo thermal and photoisomerization between Z-and E-isomers.I ts self-assembly properties in aqueous medium have been investigated by spectroscopic and microscopic techniques,demonstrating that E-and Z-azobenzenet rimers form supramolecular nanosheets and toroidal nanostructures,respectively.Byvirtue of the E/Z photoisomerization of the azobenzene units,the two different supramolecular morphologies can be switched by photoirradiation. The findings pave aw ay towards stimuli-responsive,w ater-soluble supramolecular polymers whichh old great promise in the development of smart functional materials.