A supramolecular linear-dendritic copolymer consisting of a polystyrene backbone and hanging hyperbranched polyglycerols was prepared and characterized. Host–guest interactions between β-cyclodextrin incorporated in the core of polyglycerol as a host and aromatic rings of polystyrene as guests lead to the formation of a supramolecular linear-dendritic copolymer. Supramolecules formed micelles in aqueous solutions which were able to encapsulate and transfer paclitaxel with a high loading capacity.