Recently, we reported the interesting reducing properties of the TMSCl/NaI association in CH2Cl2 towards various functional groups as unsymmetrical -diketones, -ketoesters, and hydrazones [Error! Bookmark not defined.] derivatives. Under similar reaction conditions, we next demonstrated that a variety of dithioacetals were cleanly desulfurized at room temperature in CH2Cl2 using this metal-free process in a Mozingo-type reaction. By replacing CH2Cl2 by CH3CN as the reaction solvent, we surprisingly observed that dithianes derivatives were not reduced into methylene substrates but were totally and cleanly deprotected into ketones. It seemed interesting to study in detail this method for the deprotection of thioacetals which does not use metal salts, nor oxidants, nor toxic or expensive reagents (Figure ). Herein, we wish to report the mild deprotection conditions of a range of dithianes, dithiolanes and oxygenated derivatives using the TMSCl/NaI association in CH3CN.