The first organometallic miktoarm star copolymer, PFS(PI)(3) (PFS = polyferrocenyldimethylsilane, PI = polyisoprene) with PDI of 1.04 was synthesized through anionic polymerization by using SiCl4 as the coupling agent and its well-defined structure was characterized by using GPC and H-1 NMR spectroscopy. In contrast to analogous diblock copolymers with similar PFS volume fractions which self-assemble to form cylindrical structures, PFS(PI)(3) formed unimolecular micelles in the PI selective solvent, hexane.