The present invention is directed toward water-soluble supramolecular self-assemblies and a process for their preparation via micellization of polyelectrolytes through the use of hydrophobic monomeric units. In this invention the polyelectrolyte segment ultimately forms the core of the supramolecular assembly whereas the shell consists of uncharged hydrophilic polymers or oligomers. It has been determined that the inclusion of the hydrophobic co-monomers to the polyelectrolyte segment forming the micelle core leads to a structure of enhanced stability.