Rate constants for the reactions of OH radicals and Cl atoms with diethyl sulfide (DES), di‐n‐propyl sulfide (DPS), and di‐n‐butyl sulfide (DBS) have been determined at 295 ± 3 K and a total pressure of 1 atm. Hydroxyl radical rate data was obtained using the absolute technique of pulse radiolysis combined with kinetic spectroscopy. The chlorine atom rate constants were measured using a conventional photolytic relative rate method. The rate constant for the reaction of Cl atoms with dimethyl sulfide (DMS) was also determined. The following rate constants were obtained: (Formula Presented.)