An efficient copper-catalyzed asymmetric ring-opening reaction of diaryliodonium salts with imides has been developed, affording a wide range of axially chiral 2-imidobiaryl compounds with excellent enantioselectivities and better convertibility. The potential utility of the current method has been supported by the synthesis of two known chiral ligands with better efficiency, which would be of great significance to the development of other catalytic asymmetric reactions.