Photolysis of 2-amino-2′-azidobiphenyls in diethylamine gave 4, 10-dihydroazepino [2, 3- b] indoles (7), the structure of which corresponded to the didehydroazepines formally trapped with an internal amino group. However, the yields of 7 were considerably low, which was due to the significant intramolecular interaction of the photolytically generated nitrene with an amino group, to afford benzo [c] cinnoline as a final product.