In this work, we report the self-assembly in heptane of omega-dimethyl ammonium tetrakis-pentafluorophenyl borate polyisoprenes into micellar aggregates and the use of these nano-objects to support alkylated metallocenes toward ethylene polymerization. Dynamic light scattering was used to demonstrate the self-assembly and the formation of the micellar structures having a core of polar dimethyl ammonium tetrakis-pentafluorophenyl borate moieties, and a corona of polyisoprene (PI). The latter were then used as organic supports for alkylated metallocenes to produce unprecedented millimetric polyethylene beads without loss of catalytic activity.