Girard's reagents were used to derivatize ketosteroids and conjugates for analysis by positive ion fast atom bombardment mass spectrometry. Spectra contain an abundant ion corresponding to the cation (C+) of the newly formed ionic derivative (C+A-) and relatively little fragmentation. With derivatization, detection of ketosteroids at a concentration of 1 microgram microliter-1 in glycerol was straightforward. Such derivatization schemes may prove useful in the analysis of ketosteroids in complex biological mixtures.