A method for the trace analysis of aliphatic and alicyclic amines is presented. It involves derivatization of the amines to the corresponding amides by reaction with a perfluoro fatty acid anhydride. The amines were separated by glass capillary gas chromatography and picogram amounts were quantitated using on-column injection and electron-capture or nitrogen-selective detection. The method was applied to amines of interest from work environment health aspects. Detection limits were in the 2–30 fmol range with electron-capture detection and in the 40–60 fmol range with nitrogen-selective detection. Linear ranges for the quantitative analysis were established and electron impact and methane chemical ionization mass spectra of investigated heptafluorobutyric acid amides were registered and discussed.