The field ionization and electron impact mass spectra of eleven coumarins have been compared. In the field ion spectra thc molecular ions were the base peaks and structurally diagnostic fragment ions formed by direct cleavage were present, whereas the molecular ions were weak in the electron impact spectra and fragment ions formed by rearrangement were dominant. Crude coumarin mixtures obtained from natural sources have been successfully examined using field ionization and gas chromatography + field ionization mass spectrometry.