A new type of amphiphilic macromolecule was synthesized through the attachment of a poly(ethylene glycol) chain to a permethyl-amino-beta-cyclodextrin ring. The structure of the product was studied with 1D and 2D NMR experiments and with MALDI-TOF MS. The resulting comet-shaped molecule showed self-assembly behavior in polar solvents. The presence of supramolecular structures in aqueous media was detected with dynamic light scattering and proven also by 2D NOESY and DOSY experiments. The supramolecular structures that formed could serve as starting materials for new types of drug delivery bioconjugates containing two independent dopable sites, that is, the cyclodextrin ring and the core of the supramolecular structure. (c) 2007 Wiley Periodicals, Inc.