A series of water-soluble supramolecular assemblies were constructed from dithienylethene-modified permethyl-β-cyclodextrins and porphyrin derivatives, accompanied by a high FRET efficiency, and could be applied in the control of singlet oxygen generation in a 1% ethanol aqueous solution upon irradiation of different wavelength light. These findings will provide a feasible and convenient way to construct a potential photodynamic therapy material.