AbstractCation and anion formation from molecular SF6 and SF6 clusters is reported in the F 1s-excitation regime (680–720 eV) using tunable synchrotron radiation. Stable products are identified by mass spectrometry, while the tunablility of the soft X-rays source is used to determine mechanistic details on the formation of the detected charged products. Characteristic differences are observed between product formation from the isolated molecule as well as from clusters for both, cations and anions. Specifically, dication formation, such as SF22+, is only observed for molecular precursors, which are formed with high efficiency at the F 1s → t2g-transition. SF6− is efficiently formed from clusters upon F 1s → t1u-transition. Mechanistic details on the formation of stable products are discussed.