Abstract: Three small peaks 4', 6' and 8' in the aliphatic part of ¹³C-NMR spectrum of polybutadiene (PBD) have been observed. Their appearance is considered to be related with the peaks 4,6 and 8 of the isolate 1,2-unit in PBD and to be a result of the splitting of the latter three peaks, respectively. In order to explanation these results authors of this paper consider that there must exist a new, with a higher energy level, configuration,which would show a certain shielding effect on the C_α and C_γ but decrease the shielding effect on the C_β of the isolate 1,2-unit of PBD chain.