We report the (S)-2,15-Cl₂-DHTP-catalyzed enantioselective conjugate addition of organic boronic acids to β-enaminones, providing the corresponding addition products in high yields and moderate to excellent enantioselectivities (up to 98% ee). This catalytic system exhibits unique features in terms of mild reaction conditions, high efficiency, broad substrate scope, and the applicability of alkenylboronic acids and heteroarylboronic acids.