The corona discharge used to generate positive and negative ions under conventional atmospheric pressure chemical ionization (APCI) conditions also provides a source of low-energy 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 (MS). This technique, which has been named electron-capture APCI (ECAPCI)/MS, mass spectrometry provides an increase in sensitivity of two orders of magnitude when compared with conventional APCI methodology. It is a simple procedure to tag arachidonic acid- and linoleic acid-derived oxidized lipids with an electron-capturing group such as the pentafluorobenzyl (PFB) moiety before analysis. PFB 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 PFB radical. A similar process occurs under ECAPCI conditions. By monitoring the negative ions that are formed, it is possible to obtain extremely high sensitivity for PFB derivatives of oxidized lipids derived from arachidonic and linoleic acid. A combination of stable isotope dilution methodology and chiral liquid chromatography-ECAPCI/MS makes it possible to resolve and quantify complex mixtures of regioisomeric and enantiomeric oxidized lipids.