A highly regioselective C–C bond cleavage/double cyclization of α‐ketoamides with o‐phenylene diamines has been developed for the synthesis of benzimidazo1,2‐cquinazolin‐6‐ones. Two new C–N and one new C=N bonds are simultaneously formed in the reaction, providing the gateway to access these fused heterocyclic scaffolds via copper catalysis under air atmosphere. This new protocol provides a novel and important foundation for the preparation of these heterocycles. α‐Ketoamides have been successfully employed to synthesize benzimidazo1,2‐cquinazolin‐6‐ones through C–C bond cleavage/double cyclization, in which two new C–N and one new C=N bonds are simultaneously formed by copper catalysis under air atmosphere. This new protocol provides an important foundation for the preparation of benzimidazo1,2‐cquinazolin‐6‐ones in high yields.