Starting from ferrocene, pentafluoroferrocene [Fe(C5F5)(C5H5)] can be prepared in five steps via a one-pot lithiation-electrophilic fluorination strategy. Pentafluoroferrocene was characterized by multinuclear NMR and IR spectroscopy, by cyclovoltammetry as well as X-ray (solid) and electron diffraction (gas) and the experimental results compared with DFT calculations.