<p>The oxidative C–S bond cleavage of organosulfur compounds was efficiently achieved with <i>trans</i>-5-hydroperoxy-3,5-dimethyl-1,2-dioxolan-3-yl ethaneperoxate/KOH system. Singlet oxygen (¹O₂) was the main active oxidant employed in this process, and it was produced through the fragmentation of <i>trans</i>-5-hydroperoxy-3,5-dimethyl-1,2-dioxolan-3-yl ethaneperoxate with the assistance of KOH. The current protocol provides a simple and selective method for the oxidative cleavage of C–S bonds in organosulfur compounds. All the reactions were smoothly performed at ambient temperature to produce the corresponding carbonyl compounds in quantitative yields within short reaction times.</p> Graphical abstract <p></p>