Two kinds of vanadium catalyst were prepared by the reaction of VOCl3, ROH(R=CH(CH3)C(CH3)3, CH2C(CH3)3) and AliBu3. Both catalysts were able to produce alternating copolymer of 1,3-butadiene and propylene (PBR). The spectroscopic structures of obtained copolymers appeared to be almost the same, but the thermal properties of them were different from each other. The copolymer produced by the catalyst having a chiral carbon showed a melting point at 5 °C, which was not observed in the copolymer by other catalyst. This result indicates that the stereoregularity was dramatically improved by the catalyst with a chiral carbon in alternating copolymerization of butadiene and propylene.