Dissociation upon sulfur 𝐾-shell excitation or ionization of SF6 is studied by sulfur 𝐿-shell emission spectroscopy using synchrotron radiation and multiconfiguration Dirac-Hartree-Fock calculations of emission energies and transition rates. The decay path involves in particular Auger emission with the ejection of one or more electrons, leading to singly or multiply charged intermediate states. Nevertheless, the results of the study show that the observed photon emission at 151–152 eV following excitation at 2485–2489 eV originates dominantly from transitions in neutral sulfur. This clearly indicates that the central atom retains its electrons in a dissociation process where all fluorine atoms detach before the S 2⁢𝑝 decay.