ABSTRACTAnalytical supercritical fluid extraction (SFE) has been utilized to characterize the volatile content of oxidized vegetable oils. A major advantage of SFE is that the temperatures employed in the extraction reduce the probability of hydroperoxide decomposition. To test the SFE‐based method, canola, corn, soybean and sunflower oils were stored at 60C for 16 days in loosely capped bottles. The volatiles content of each oil was then desorbed by using supercritical CO2for extraction directly onto a gas chromatographic column where they were subsequently analyzed by gas chromatography‐mass spectrometry. Extraction conditions of 50C and 1500 psi were utilized for both the zero‐time oils and the oxidized oils to determine the change in concentration of the individual volatile compounds. Peroxide values (PV) were also determined for each oil and these ranged from 0.4 to 1.1 meq/kg for the zero‐time oils and from 52 to 82 meq/kg for the samples aged 16 days. These PV values all correlated well with the increase in concentration of several volatile compounds. Hexanal, the largest volatile peak found in the zero‐time oils, measured 0.4–0.6 ppm but increased to 52–366 ppm in the highly oxidized oils. Corn oil was the only oil that had measurable amounts of 2,4‐decadienal isomers at the initial sampling time. However, after storage, the decadienal isomers were found to be major volatile components in the total volatiles profile for all of the oils. The described SFE method proved to be a rapid and benign technique and very effective for determining the extent of oxidation in