Well-defined poly(vinylferrocene)s with predictable molecular weights and low polydispersities were prepared by living anionic polymerization of vinylferrocene initiated with (BuLi)-Bu-n in tetrahydrofuran (THF) at -28 degrees C as well as 0 degrees C. The living poly (vinylferrocenyl)lithium (PVFcLi) was first employed in coupling reactions with haloallyl chain-end functionalized polyisobutylene (PIB) series. By using bromoallyl chain-end functionalized PIB, the coupling proceeded in THF at 0 degrees C to afford a new AB diblock copolymer comprised of PIB and PVFc segments with high coupling efficiency (similar to 85%) limited by undesired lithium-halogen exchange. The synthesis of an ABA triblock copolymer, PVFc-b-PIB-b-PVFc, was also attempted by coupling of cc,(alpha,omega-bromoallyl difunctionalized PIB and PVFcLi; however, lithium-halogen exchange yielded a significant amount of byproducts. In contrast, PIB-b-PVFc and PVFc-b-PIB-b-PVFc with excellent coupling efficiencies (>94%) could be successfully synthesized by using chlorosilyl chain-end functionalized PIB in coupling reactions with PVFcLi. The polymers were characterized by gel permeation chromatography (GPC)-multiangle laser light scattering (MALLS) and proton nuclear magnetic resonance (H-1 NMR) analyses. The differential scanning calorimetry (DSC) thermogram of PVFc-b-PIB-b-PVFc showed two glass transition temperatures at -65 and 198 degrees C, suggesting microphase-separated morphology. Transmission electron microscopy (TEM) corroborated the typical disordered spherical morphology of a PVFc-b-PIB-b-PVFc thin film. The stress-strain plot of a solution cast sample of PVFc-b-PIB-b-PVFc showed typical elastomeric property.