AbstractThe Michael reaction is a conjugate addition and is one of the most powerful methods with which to prepare functional molecules with a β‐stereogenic center. Despite its success in the formation of various asymmetric carbon–carbon and carbon–heteroatom bonds, enantioselective seleno‐Michael addition remains essentially unexplored. We report here a highly enantioselective Michael addition reaction of alkyl selenols to enones. This method conveniently introduces a Se atom to an electron‐deficient double bond asymmetrically. A chiral bifunctional N‐heterocyclic carbene (NHC)/thiourea catalyst was developed as a key ingredient that delivers chiral β‐seleno ketones with remarkable selectivity. This new catalyst and its mode of action support broad applications in the catalytic activation of nucleophilic reactions.