α-Functionalized polybutadiene(PBD) having tert-aromatic amine group at on e end was prepared by the stoichiometric reaction between sec-butyllithium and 1,1'-bis[4-diethylaminophenyl]ethylene(BDEAPE). The tert-aromatic amine function alized yield was over 92 mol% based one the ratio 1H-NMR spectroscopic analysis. And tributyltin functionalized PBD was synthesized utilizing tributyltin chloride as an end-capping reagent, in which the functionalization yield was over 91 mol%. These α-functionalized PBD was coupled with tin tetrachloride to form a branched α, ω-functionalized PBD, in which the molecular weight distribution could be controlled by the coupling %. The molecular weight distribution of the above polymers was controlled by tin coupling reaction using tin tetrachloride.