Supramolecular miktoarm stars (AB(2) type) composed of poly (methyl methacrylate)-polystyrene(2) (PM MA-PS. poly(isoprene)-polystyrene2 (PI-PS2), and poly(vinyl acetate)-polystyrene, (PVAc-PS2) were successfully synthesized by assembling reversible addition fragmentation chain transfer (RA FT)-polymerized chains bearing hydrogen-bonding heterocomplementary associating units To this end, thymine and diaminopyridine-Functionalized chain transfer agents were designed to efficiently mediate the polymerization of vinyl acetate, methyl methacrylate. isoprene, and styrene The selective associations of the resulting hydrogen-bonding macromolecular building blocks PVAc/PS. PI/PS, and PMMA/PS were demonstrated by H-1 NMR in CDCl3 solutions Miktoarm stars formation in the bulk was also confirmed by transmission electronic microscopy