Abstract Chiral sulfoximines have significant roles in pharmaceutical industry and agricultural chemicals. Furthermore, chiral structurally related sulfoximines are used for their wide potential applications in some uncharted territory. However, chromatographic study on these compounds has not been systematically performed. Herein, this paper describes the enantioseparation of 12 chiral sulfoximines on polysaccharide-based chiral stationary phases (CSPs). Separation factors of chiral column, high-performance liquid chromatography parameters such as mobile phase composition and column temperature were carefully investigated. Chiralcel OJ-H column can resolve all of the 12 compounds, while Chiralpak AD-H column and Chiralpak AS-H column can separate eight and nine molecules, respectively. The sulfoximines are effectively resolved with Chiralcel OJ-H column with a mixture of n-hexane/2-propanol (80:20) as the mobile phase.