Analytical methods for oxygenates in exhaust gases were studied, and emissions of these compounds from automotive engines were measured with and without an oxidation catalyst in the exhaust system. Hydrocarbons, simple mixtures of hydrocarbons, and a single gasoline were used as fuels. With the more complex gasoline, successful analysis was possible only with exhaust from the catalytic system with preferentially converted and thus removed interfering hydrocarbon species. However, it was shown that an estimate of the oxygenate yield from gasoline used in a noncatalytic system can be synthesized from data obtained with simple fuels. Such synthesized data were used for comparison of noncatalytic with catalytic systems. Compared with those of previous studies, results of this work indicate that the action of the catalyst introduced no new oxygenates and reduced both the carbonyl and the total of oxygenates. It is concluded that the compositional character and class distribution of oxygenates in exhaust from catalytic systems may differ significantly from the composition and distribution for oxygenates not subjected to catalytic conversion. The findings also support previous estimates that noncarbonyls may constitute a significant fraction of exhaust oxygenates and may warrant attention in procedures for measurement of the oxygenates. Work done under an agreement with the coordinating research council, air pollution research advisory committee.