Eleven phenols and 2,4-dichlorophenoxyacetic acid, compounds that may be found in body fluids of humans exposed to pesticides, are derivatized with pentafluorobenzyl bromide and characterized by gas chromatography with electron capture detection. These derivatives are further characterized by positive and negative chemical ionization mass spectrometry, nuclear magnetic resonance spectroscopy, and gas chromatography-Fourier transform infrared spectroscopy. Negative chemical ionization mass spectra of all derivatives have an anionic base peak derived from the parent analyte. In the positive mode the nonchlorinated derivatives have base peaks indicative of the analyte, while chlorinated derivatives are cleaved to give the pentafluorobenzyl cation as base peak. The possibility is explored that ortho-substituted phenols might be formed as byproducts in these derivatizations.