The corona discharge used to generate positive and negative ions under conventional atmospheric pressure chemical ionization conditions also provides a source of gas-phase electrons. This is thought to occur by displacement of electrons from the nitrogen sheath gas. Therefore, suitable analytes can undergo electron capture in the gas phase in a manner similar to that observed for gas chromatography/electron capture negative chemical ionization/mass spectrometry. This technique, which has been named electron capture atmospheric pressure chemical ionization/mass spectrometry, provided an increase in sensitivity of 2 orders of magnitude when compared with conventional atmospheric pressure chemical ionization methodology. It is a simple procedure to tag many biomolecules and drugs with an electron-capturing group such as the pentafluorobenzyl moiety before analysis. Pentafluorobenzyl derivatives have previously been used as electron capturing derivatives because they undergo dissociative electron capture in the gas phase to generate negative ions through the loss of a pentafluorobenzyl radical. A similar process was found to occur under electron capture atmospheric pressure chemical ionization conditions. By monitoring the negative ions that were formed, it was possible to obtain attomole sensitivity for pentafluorobenzyl derivatives of a representative steroid, steroid metabolite, prostaglandin, thromboxane, amino acid, and DNA-adduct.