The novel functionalized triblock copolymers, poly[(4-vinylphenyl)dimethylsilane]-b-polybutadiene-b-poly[(4-vinylphenyl)-dimethylsilane] (PVPDMS-b-PBd-b-PVPDMS), were synthesized by anionic polymerization method using high vacuum technique. The hydrocarbon-soluble dilithium initiator synthesized from 1,3-di[ l-(methylphenyl)ethenyl]benzene (MPEB) was used to synthesize polybutadiene (PBd) precursors and the triblock copolymers in the presence of sec-BuOLi. The precursors and copolymers were characterized by size exclusion chromatography (SEC),1HNMR and DSC techniques.