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The interaction between oppositely charged ionic polymers results in the formation of interpolyelectrolyte complexes (IPECs), which represent macromolecular co-assemblies stabilized mainly by salt bonds between their polymeric components. IPECs are of considerable interest due to numerous promising applications as advanced polymeric reagents and materials for medicine, biotechnology, ecology, etc. This contribution considers water-soluble IPECs that are based on ionic polymer species of non-linear (branched) topology (star-shaped polyelectrolytes, including bis-hydrophilic ionic/non-ionic miktoarm stars, star-like micelles of ionic amphiphilic diblock copolymers, and cylindrical polyelectrolyte brushes) complexed with linear polyions bearing the opposite charge. Depending on the branched polymeric component involved in the electrostatically driven co-assembly, the resulting nanosized complex particles can have various structural organization, i.e., (a) “core-corona” structure in the case of star-shaped homopolyelectrolytes, (b) “core-shell-corona” structure in the case of star-like micelles of ionic amphiphilic diblock copolymers, (c) “pearl necklace” structure with each pearl having “core-corona” structure in the case of cylindrical polyelectrolyte brushes, and (d) vesicular structure in the case of bis-hydrophilic ionic/non-ionic miktoarm stars, the last-mentioned being very rare for IPECs. Such water-soluble IPECs are considered as compartmentalized macromolecular co-assemblies that can be in-demand, e.g., as nanocontainers and nanoreactors, for nowadays rapidly developing nanotechnologies.