Local motions in the cyanogenic glycoside amygdalin have been characterized by variable-temperature 13C solid-state NMR spectroscopy. Carbon-13 chemical shift tensors and 1H−13C dipolar couplings were measured by advanced magic-angle spinning NMR techniques over the temperature range 0−90 °C. The main conclusions from our study are that the phenyl ring exhibits thermally activated dynamics about the para axis, whereas the glucopyranosyl residues remain immobile upon heating. It was also found that sample heating is accompanied by loss of water. The experimental results were complemented by quantum chemical calculations of the 13C chemical shift tensors, which were utilized in the analysis of the experimental NMR parameters.