The 13C NMR spectra of the natural coumarins ostruthin, osthol, aegelinol (enantiomer of decursinol), luvangetin, seselin, anomalin, oxypeucedanin (and its enantiomer prangolarin) and oxypeucedanin hydrate and some of their derivatives have been studied. Self‐consistent resonance assignments have been made following chemical shift theory and using simple models. Carbon‐hydrogen coupling constants of some compounds are also reported. The alkoxy group/s at C‐5 and/or C‐8 in linear furocoumarins, as well as in linear pyranocoumarins, have unusually small shielding effects on the ortho‐ and para‐carbons. This study also indicates that the C‐4a and C‐8 resonance assignments of osthol, made earlier, should be reversed. Copyright © 1981 Heyden & Son Ltd.