A polyfluoroalkyl substituted phthalocyanine based supramolecular light switch was assembled by the host–guest interaction between the novel polyfluoroalkyl substituted silicon phthalocyanine and pyrene-β-cyclodextrin, which was attached on the sidewalls of SWNTs through the pyrene groups. This supermolecule can not only absorb light to convert its energy into heat energy, but also respond to light, control the release of phthalocyanine and restore fluorescence and produce singlet oxygen for a synergistic photothermal and photodynamic effect against Escherichia coli.