A novel methodology (electrostatic self-assembly and covalent fixation) has been proposed for designing various nonlinear polymer topologies, including monocyclic and polycyclic polymers, cyclic macromonomers and cyclic telechelics (kyklo-telechelics), a-ring-with-a-branch topology polymers and polymeric topological isomers, as well as branched model polymers, such as star polymers and polymacromonomers. Thus, new telechelic polymer precursors having a moderately strained cyclic onium salt group as single or multiple end groups and carrying multifunctional carboxylates as the counterions were prepared through an ion-exchange reaction. A variety of electrostatic self-assemblies of these polymer precursors, formed particularly in dilute organic solution, was then subjected to heat in order to convert the ionic interactions into covalent linkages by ring-opening reaction, and to produce topologically unique, nonlinear polymer architectures in high efficiency.