Cu(II) ion-responsive self-assembly in aqueous media was achieved based on a water-soluble pillar[5]arene host and a rhodamine B-containing amphiphile guest. The host-guest complex acted as a supra-amphiphile and self-assembled into vesicles. After addition of Cu(II), vesicles turned into solid nanoparticles, accompanied by the color change of the solution from colorless to red and a fluorescence "on" phenomenon.