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The interaction of star-shaped polyions (polyelectrolyte stars) (a) with oppositely charged linear homopolyelectrolytes and (b) with oppositely charged double hydrophilic (ionic/non-ionic) diblock copolymers in aqueous media was investigated. This interaction generates nanosized compartmentalized complex species if a certain charge-to-charge stoichiometry between the oppositely charged polymeric components is met. The formed macromolecular co-assemblies have micelle-like (“core-corona”) structure. A hydrophobic core of each of the complex species is assembled from essentially equal amounts of the oppositely charged monomer units of the polymeric components. In case (a) (viz., star-shaped polyions interacting with oppositely charged linear homopolyelectrolytes), a hydrophilic corona granting the whole complex species solubility in aqueous media is composed of free (excessive) arms of the star-shaped polymeric component, which are not coupled to fragments of the oppositely charged linear homopolyelectrolyte. In case (b) (viz., star-shaped polyions interacting with oppositely charged double hydrophilic diblock copolymers), a composition of a hydrophilic corona providing solubility for the whole complex species in aqueous media is determined by a charge-to-charge stoichiometry between the oppositely charged polymeric components. It either can be built up purely from non-ionic blocks of the double hydrophilic diblock copolymer or can be composed of non-ionic blocks of the double hydrophilic diblock copolymer mixed with free (excessive) arms of the star-shaped polymeric component, which are not coupled to ionic blocks of the oppositely charged double hydrophilic diblock copolymer. Such compartmentalized complex macromolecular architectures are thought to be highly in-demand by rapidly developing nanotechnologies, for example, for a design of nanocontainers and nanoreactors.