Improved synthetic and isolation procedures have been developed that resulted in the preparation of pure C60F20 in sufficient amounts for comprehensive vibrational spectroscopic studies. The FTIR spectrum, the first Raman spectrum, and DFT vibrational calculations of the two possible D-5d-symmetry isomers of C60F20 provide compelling evidence in favor of the previously proposed Saturn-like structure of this fluorofullerene. Excellent agreement between the experimental and simulated spectra allowed a complete vibrational assignment for C60F20 to be made.