Supramolecular poly(vinyl acetate) PVAc 3-arms stars were successfully generated by Reversible Addition-Fragmentation chain Transfer (RAFT)-polymerized chains bearing hydrogen-bonding heterocomplementary associating units. Chain Transfer Agents (CTA) bearing thymine- and diaminopyridine-based units were first synthesized and proved to mediate efficiently the polymerization of VAc. The binding ability of the chains in solution was then demonstrated by H-1 NMR and GPC measurements, proving the formation of the supramolecular stars.