A novel class of crown ether-bearing [70]fulleropyrrolidines containing a benzothiazolium styryl dye has been synthesized. The compounds have been characterized by FT-IR, NMR and mass spectra. The UV–Vis absorption and fluorescence spectra of the compounds have also been studied, which show the absorption and emission peaks of the compounds can be hypsochromically shifted by alkaline and alkaline–earth metal ions complexation.