High-frequency (125 MHz) high-resolution ¹³C NMR spectra of polybutadiene with varying amounts of 1,2 units were studied. Methine and methylene subspectra were separated using DEPT (Distortionless Enhancement by Polarization Transfer) techniques. Comparison of the NMR spectra of polyalkenamers, linear polybutadiene, and related structures made it possible to calculate the substitution parameters for the carbons that are up to four bonds away from the branching junction. The assignment of ¹³C NMR signals to aliphatic carbons incorporated into the diads or triads of 1,2 or 1,4-units was made.