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Micellization of polystyrene/poly(2-vinylpyridine) heteroarm star copolymers, PSnPVPn, in aqueous media has been studied by a combination of light scattering and fluorescence techniques. Three copolymer samples differing in numbers of arms and their length form micelles with compact hydrophobic cores and polyelectrolyte poly(2-vinylpyridine) shells. The association number decreases with increasing number of water-soluble arms and their length. Micellization equilibrium is kinetically frozen in aqueous media. The micellar cores are frozen and the behavior of the micellar solutions is controlled by the polyelectrolyte behavior of the polyelectrolyte shell. In the case of the present heteroarm stars with ca. 10 1 arms, the soluble and insoluble arms are strongly segregated and the micellar cores are formed of pure polystyrene as with micelles formed by linear diblock copolymers. As concerns the sample with several tens of arms, a significant steric hindrance, together with a low association number (ca. 4), does not allow for a complete segregation of polystyrene and the poly(2-vinylpyridine) arms. The micellar cores formed by the very hairy star copolymer with several tens of arms contain a fraction of poly(2-vinylpyridine) arms as shown by fluorescence measurements with solubilized pyrene. Alkalimetric titration of an acidic mixture of PSnPVPn micelles with a linear poly(2-vinylpyridine)-block-poly(ethylene oxide) copolymer, PVP-PEO, yields fairly monodisperse spherical onion-skin micelles. The onion-skin micelle has a compact spherical PS core deriving from the parent PSnPVPn micelle, a fairly thin and compact middle layer formed by PVP both from the parent micelle and PVP-PEO copolymer, and a protective PEO shell. The formation of onion-skin micelles is fully reversible and occurs suddenly and very rapidly at pH values higher than 4.8. The "onions" dissociate immediately into PSnPVPn micelles and PVP-PEO copolymer below pH 4.8. Evaluation of the alkalimetric titration data shows that only ca. 40% of the PVP units in the micellar shells are protonized (even in strongly acidic solutions that contain a large surplus of a strong acid, e.g., in 0.1 M HCl). This observation is in agreement with indirect fluorometric data which indicate that in the case of a weak polyelectrolyte, such as poly(2-vinylpyridine), the inner layer of the polyelectrolyte shell close to the core is not ionized.