Two water-soluble polymers poly(2-methyl-2-oxazoline) and poly(N-isopropylacrylamide) with complexing moieties (beta-CD and adamantane, respectively) located at the chain ends were prepared via controlled techniques. To verify the interaction of the beta-CD- and adamantane-type polymer end groups in aqueous solution, detailed complexation studies were carried out by H-1 NMR spectroscopy. It could be proved, that the polymers undergo self-assembly to form the corresponding supramolecular diblock structure. Furthermore, the double-hydrophilic block assembly was observed to be switchable to a hydrophilic-hydrophobic configuration by adjusting temperature leading to reversible aggregate formation.