A new series of fluorinated amphiphilic β-cyclodextrin derivatives has been synthesized. The strategy is based on the modification of the C-6 position of the mono-6-deoxy-6A-para- tolylsulfonyl, di-6A, 6D-deoxy-6A, 6D-(para-tolylsulfonyl) and heptakis-(6-deoxy-6-iodo)-β- cyclodextrin precursors. The synthesis lead to mono-perfluoroalkylthio-, di-perfluoroalkylthio- and heptakis-perfluoroalkylthio-β-cyclodextrin in excellent yields (90–99%).