The negative and positive ion fast atom bombardment mass (FAB) spectra and fast atom bombardment mass-analysed ion kinetic energy/collision-activated dissociation (MIKEKAD) spectra of triterpenic saponins (triterpenic glycosides) are reported. That ionization technique is well suited to the analysis of natural mixtures of these compounds. Identification and sugar sequences can be obtained from the conventional MIKE and MIKEICAD spectra. It is shown that the negative FAB mass spectra with polyethylene glycol 200 as the matrix givt? more informatfon than positive spectra for this family of compounds. The negative ion FAB mass spectra sh& intense deprotonated molecular peaks [M-Hl-which shift to [M+Cl]-in a polyethylene glycol 200MH,Cl matrix. The positive ion FAB mass spectrometry with glycerol/NaCl as a matrix gives spectra characterized by an enhanced sodium cationized molecular ion [M + Na]'.