We present the synthesis of supramolecular star polymers with heterogeneous chemical compositions through potassium cation-templated assembly of guanosine end-functionalized random, diblock, and Y-shaped copolymers. The assembly and disassembly processes of the synthesized star polymers have been systematically examined on changing the concentration, the temperature, the solvent, and the amount of cation using 1H NMR, UV/vis, and CD spectroscopy. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012