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Since the soccer-ball-shaped molecule C60 and other fullerenes became available in macroscopic quantities, a wide variety of derivatives with multiple C–F bonds have been generated and observed in the gas phase. A significant number of these have also been isolated in weighable amounts and characterized by spectroscopic, electrochemical, and diffraction techniques. Those that have had their structures unambiguously determined by single-crystal X-ray diffraction include the fluorofullerenes C60F18, C60F36, and C60F48; the trifluoromethyl derivative C60F17(CF3) the oxafluorofullerene C60F18O; and the organofluorofullerene C60F15[CBr(CO2Et)2]3. In this article, the major developments in fluorofullerene chemistry will be reviewed, including the synthesis and characterization of selectively fluorinated fullerenes and their physical properties and chemical reactivities that will be important in their consideration for technological applications.