In this work, we report how micellar structures obtained by the self-assembly in heptane of polyisoprene end-capped with a hindered tertiary alcohol moiety (PI-phi(2)OH) can be efficiently used as organic supports for olefin polymerization single-site catalysts. PI-phi(2)OH has been synthesized by end-capping living polyisoprenyllithium with an excess of benzophenone. Dynamic light scattering analysis indicates a self-assembly of PI-phi(2)OH in heptane, a good solvent for polyisoprene and a poor one for the polar end-group. The so-formed micelle-like nanoparticles, composed of a di-phenyl alcohol group core and a polyisoprene corona were used as organic supports for catalytic system composed of aluminic activators, trimethylaluminium (TMA) or methylaluminoxane (MAO), and metallocene or post-metallocene catalysts, to produce micrometric polyethylene beads.