The synthesis and characterization of unique polyhalogen cations containing μ-bridging fluorine atoms are reported. The [Br2F5]+ cation features a symmetric [F2Br-μ-F-BrF2] bridge, whereas the [Br3F8]+ contains asymmetric μ-F bridges. These fluoronium ions, obtained as [SbF6]- salts, were investigated using Raman and 19FNMR spectroscopy, as well as single-crystal X-ray diffraction. Quantum chemical calculations were carried out for the gas-phase cations as well as for the solid-state compounds. Population analyses show the μ-F atoms to possess the most negative partial charge within the cations.