We report the results of the theoretical study of (OH)-O-center dot-induced oxidative cleavage of dimethyl disulfide (DMDS) and the experimental study of the CH3SSCH3 + (OH)-O-center dot reaction in the presence of (NO)-N-center dot. Infrared low temperature argon matrix studies combined with ab initio calculations allowed us to identify cis-CH3SONO, which evidences the formation of the CH3SO center dot and CH3SH molecules in the course of the CH3SSCH3 + (OH)-O-center dot reaction. Ab initio/quantum chemical topology calculations revealed details of the oxidative cleavage of dimethyl disulfide, which is a complex multistep process involving an alteration of S-O and S-S covalent bonds as well as a hydrogen atom transfer. The ability of delocalization of the unpaired electron density by sulfur atoms and a formation of a hydrogen bond by CH3SO center dot and CH3SH are the factors which seem to explain antiradical properties of DMDS.