The chemical shifts were calculated for diastereomers of 2,4,6,8,10,12,14,16,18-nonaethylnonadecane (NEND), in which the methylene C9 and methine C10 of the backbone chain and methylene C10 and methyl C10 of the side chain serve as models of CH2 (backbone), CH, CH2 (side chain), and CH3 of poly(1-butene) (PB), respectively. The so-called γ effect and Suter–Flory rotational isomeric model were taken into account in the calculation. Additional repulsive interaction, τ*=0.6 between the ethyl group of the side chain and backbone was also considered when both adjacent backbone bonds were trans. The γ interaction was clarified to be important between the methylene carbons of the backbone chain and methyl carbons of the side chain. The methylene (tetrad) and methine (pentad) carbons of the backbone chain and the methylene (pentad) and methyl (pentad) carbons of the side chain of isotactic PB were successfully assigned to stereosequences by a comparison with the calculated spectra of NEND. A similar calculation was done for the chemical shifts of the methylene C9, methine C10, and methyl C10 of 2,4,6,8,10,12,14,16,18-nonamethyl nonadecane as a polypropylene (PP) model in order to determine the propriety of the calculated chemical shifts for NEND by comparison. Agreement between the calculted and observed chemical shifts of all carbons was excellent for both PB and PP.