Site-selective information about local segmental motions of individual CHn fragments can be obtained by the determination of C-13-H-1 heteronuclear dipolar couplings. A systematical study was performed by measuring heteronuclear residual dipolar couplings of natural rubber samples with different cross-link densities using static and MAS solid-state NMR techniques such as SEDOR (spin-echo double resonance), REDOR (rotational-echo double resonance) and heteronuclear double-quantum (HeDQ) buildup curves. Even under static conditions, all five CHn fragments of the monomer unit can be separated. C-13-H-1 residual dipolar couplings and scaled average order parameters extracted from the different experiments show a linear correlation with the cross-link density. However, the residual dipolar couplings are also dependent on the individual functional group. In other words, the local rotational motions of the functional groups are superimposed on the segmental motions of the chain segment and have to be taken into account in the prediction of the dynamic order parameter. From our analysis, the REDOR experiment gives the most reliable results and shows the largest dependence on the cross-link density. Because of the small residual dipolar couplings, the heteronuclear J-coupling cannot be neglected in the analysis of the experimental data. The described methods can also offer site-selective information for soft solids with even larger values of the cross-link density than those investigated in this study.