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 ...