Axially chiral diaryl ethers are important structural motifs, but their catalytic atroposelective construction remains challenging due to the low racemization barrier of the C-O axis. This work introduces an N-heterocyclic carbene (NHC)-catalyzed desymmetrizative amidation strategy for the direct enantioselective synthesis of C-O axially chiral benzoimides. The reaction employs readily available aryl amides and axially prochiral diaryl ether dialdehydes and proceeds under mild conditions to deli