We disclose herein an asymmetric synthesis of axially chiral oxazepine-containing bridged biaryls via CPA-catalyzed kinetic asymmetric alcoholysis. Control experiments showed that this CPA-catalyzed alcoholysis was reversible, and lowering the reaction temperature could almost suppress the reversible reaction, thus providing a series of axially chiral oxazepine-containing bridged biaryl compounds in good to excellent enantioselectivities. The gram-scale reactions and facile derivatizations of the enantioenriched products demonstrate the practical utility of this reaction.