A general method for the catalytic asymmetric α-selenenylation of simple carbonyl compounds is lacking. Herein, a copper(I)-catalyzed enantioselective α-selenenylation of 2-acylimidazoles with electrophilic selenosulfonates is uncovered. The reaction enjoys the advantages of mild conditions, easy reaction protocol, and broad substrate scopes on both 2-acylimidazoles and selenosulfonates. Mechanistic studies reveal a pincer Cu(I)-(