Chiral sulfinamides are increasingly recognizedfor their extensive potential applications in chemistry, medicine and material science, yet chromatographic study on these compounds is seldom. In this article, we describe the enantioseparation of twelve closely related chiral sulfinamide derivatives on polysaccharide-based chiral stationary phases (CSPs). We investigated the factors affecting separation, such as the types of chiral columns, the concentration of polar alcohol and the column temperature. The acyclic sulfinamide derivatives-with the exception of a cyclic sulfinamide compound-were effectively resolved with a Chiralcel OD-H column and a mixture of n-hexane:isopropyl alcohol (90:10) as the mobile phase. All compounds except N-benzylidene-2-methylpropane-2-sulfinamide are baseline resolved on the Chiralpak AD-H column, but only eight compounds are resolved on a Chiralpak AS-H column under the given chromatographic conditions. This study offers valuable guidance for future chiral HPLC studies related to chiral sulfinamides.