The influence of olefins on the oxidative desulfurization of model mixtures and catalytically cracked gasoline has been studied. It has been established using model mixtures and a wide-cut fraction of catalytically cracked gasoline that the presence of olefins in fuel suppresses the oxidative desulfurization process as a result of occurrence of side oxidation reactions of unsaturated compounds. It has been shown that under the given conditions, it is preferable to use neutral catalysts based on transition metal salts for the oxidative desulfurization, rather than catalysts of acidic nature.