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Owing to the important utilities in many areas, the preparation of chiral sulfur-containing compounds has attracted special attention of chemists. As an alternative of the most popular asymmetric sulfur-Michael addition, asymmetric α-sulfenylation has been developed well in recent years. This short review would summarize the advance on asymmetric α-sulfenylation. Two asymmetric protocols, including transition-metal catalysis and organocatalysis, are discussed respectively.