A series of fluorinated derivatives have been examined for their suitability of use for quantification of biogenic trace amiaes, in particular phenylethylamine, in biological samples at the picogram (femtomolar) level using aegotive ion ma= spectrometry. The negative ion mass spectra of the pentafluoropropionyl, heptafluorobutyryi, perfluorasuccinimido, pentafluorobemyl and pentafluorobemoyl derivatives of phenylethyhmine are characterized by intense high-mass fragment ion peaks due to loss of HF, whereas the spectra of the 3-trifluoromethylbemoyl, Qtrifluorometbylbenzoyl and 3,5-di-trifluoromethylben~yl derivatives exhibited fragment ions due to loss of H or 2H and the pentafluorobemoyl derivative did not form a detectable molecular ion. After acetylating the fluorobenzoyi derivatives of phenylethylamine, the spectra of the resultant amides were found to contain primarily molecular ions, and the electron capture cross-sections and negative ion sensitivities increased. The most suitable derivatives were fouud to be the N-acetyl-N-pentafluorobenzoyl, which could be detected at the 75 fg (0.5 attomolar) level of phenylethylamine and the N-acetyl-N-3,!5di-(trifluoromethy1)beayl derivative.