Fluorinated groups are essential hydrophobic groups in drug design. Combining a carbon-free tetrafluoro-λ6-sulfanyl (SF4) group with a polyfluoroalkyl group (RF) provides SF4RF groups, exhibiting high hydrophobicity with a short carbon chain. In this study, various aryltetrafluoro(polyfluoroalkyl)-λ6-sulfanes (ArSF4RF) were synthesized through the radical addition of arylchlorotetrafluoro-λ6-sulfanes (ArSF4Cl) to tetrafluoroethylene. In addition, quantification of hydrophobic constants (πPh) indicated that the SF4 group is considerably more hydrophobic than a difluoromethylene (CF2) group. Further transformation reactions revealed the stabilities and reactivities of these novel fluorinated groups. The high hydrophobicity and synthetic utility of the SF4RF group lead to the potential applications of the SF4RF group in the pharmaceutical field.