An "electrostatic self-assembly and covalent fixation" process has been applied with linear and three-armed star telechelic polymer precursors carrying a mixture of mono- and dicarboxylate counteranions. It has been shown that a unimeric polymer assembly is formed exclusively with the linear polymer precursor under appropriate dilution through the effective discrimination of mono- and dicarboxylate counteranions with balancing the charges between cations and anions. Subsequently, a selective synthesis of tadpole polymers has been achieved with the three-armed star telechelic precursor carrying a pair of a mono- and a dicarboxylate counteranion. Moreover, functional tadpole polymers possessing a hydroxy group at the precisely designated position have been prepared by the use of hydroxy-containing mono- and dicarboxylate counteranions.