The gas-phase homolytic S–F bond dissociation energies (BDEs) of 21 sulfenyl-type fluorides (RSF) have been obtained using the W1w thermochemical protocol. The BDEs (at 298K) for the species in this set range from 316.2 (HCCSF) to 368.1 (H2CCHSF) kJ mol–1. We additionally report fluorine-transfer energies (FTEs), corresponding to the energetics of fluorine transfer from RSF to H2S. At 298K, the FTEs range from –10.7 (H2AlSF) to 90.7 (MeHNSF) kJ mol–1. We have also assessed the performance of a wide range of density functional theory (DFT) and double-hybrid DFT methods (in conjunction with the A'VQZ basis set) for the calculation of these quantities. For the calculation of S–F BDEs, the M06-2X procedure offers the best performance, with a mean absolute deviation (MAD) of 1.6kJ mol–1, whilst for the FTEs, B2K-PLYP and DSD-PBEP86 offer the best performance with MADs of 0.5kJ mol–1.