An amphiphilic phosphodiester-linked azobenzene trimer has been exploited in the development of stimuli-responsive, water-soluble supramolecular polymers. The trimer can reversibly undergo thermal and photoisomerization between Z- and E-isomers. Its self-assembly properties in aqueous medium have been investigated by spectroscopic and microscopic techniques, demonstrating that E- and Z-azobenzene trimers form supramolecular nanosheets and toroidal nanostructures, respectively. By virtue of the E/Z photoisomerization of the azobenzene units, the two different supramolecular morphologies can be switched by photoirradiation. The findings pave a way towards stimuli-responsive, water-soluble supramolecular polymers which hold great promise in the development of smart functional materials.