Polybutadiene (BR) was pyrolyzed at $540-860^{circ}C$ and the effect of pyrolysis temperature on variations in the relative abundance of the major pyrolysis products (C4-, C5-, C6-, C7-, and C8-species) was investigated. Formation of the C4-, C5-, C6-, and C7-species competed with that of the C8-species. Relative intensity of the C8-species decreased with increasing pyrolysis temperature, while that of the C5-, C6-, and C7-species increased. Pyrolysis paths were became more complicated with increasing pyrolysis temperature. We suggested the operation of double bond migration and succeeding rearrangements for the formation of the C5- and C7-species and various rearrangements, including a double bond, for the formation of the C6-species at high temperature. The activation energies for the pyrolysis product ratios of(C5+C6+C7)/C4 and C8/C4 were used to explain the competition reactions to form the pyrolysis products.