Fast atom bombardment (FAB) followed by collisional activation (CA) mass spectrometry was used for structural analysis of steroidal oligoglycosides, containing two to four sugar units. In the molecular ion region of the FAB mass spectra of these underivatized natural products, intense protonated molecular ions were observed. The collisional activation spectra of these mass selected ions yield more sequence information than FAB mass spectra and are not contaminated with interfering peaks originating from impurities or matrix.