A new series of amphiphilic cyclodextrins containing cationic groups at the 6-positions and alkyl or biolabile ester groups at the 2-positions has been synthesised. Selective 2-O-allylation followed by photochemical addition of lipophilic thiols made it possible to control lipophilicity in these mesomolecules and allow solubility and self-assembly in water. The cationic groups are cysteamine-derived, while the alkyl and ester groups are C₁–C₁₆ and benzyl ester groups. This is a new general synthetic route to a potentially wide range of polycationic cyclodextrins capable of acting as gene delivery vectors by condensing DNA and forming liquid crystalline complexes with oligonucleotides.