It is known that trans-1,4-polybutadiene shows a crystal transformation at about 76°C. The crystal structure of the high-temperature form of trans-1,4-polybutadiene has been studied by X-ray diffraction. The chain conformation of the high-temperature form is similar to that of the low-temperature form. Above the crystal transformation temperature, the CH2─CH2bond remains trans, but the internal rotation angles around two CH2─CH bonds are decreased to 80° and −80° from 109° and −109°, respectively. The molecular chains, however, are considered to be in a considerably distorted state due to torsional oscillation about the C─C bonds. It is shown that the X-ray diffraction pattern of the high-temperature form can be explained by taking into account the rotational motion of the chain segments around the molecular axes.