The Co(III)-catalyzed reaction of 1,3-dicarbonyl compounds with 2-(diazoacetyl)-2H-azirines, prepared by a simplified procedure from 2H-azirin-2-carbonyl chlorides, led in high yields to the formation of 2-(diazoacetyl)pyrroles, while leaving the diazoacetyl function intact. The intramolecular aromatic substitution reaction of 2-(diazoacetyl)pyrroles, catalyzed by Cu(OTf)2, provided selectively previously unknown benzo[e]- and hetero[e]-fused indol-7-oles in good yields. Formylation of benzo[e]indol-4-ol led selectively to the 5-formyl derivative, which is a good precursor for an unusual salen ligand and its Ni-complex. Triflates prepared from benzo[e]indol-4-oles gave various 4-substituted benzo[e]indoles carrying aryl, 2-thienyl, 2-pyridyl, and alkynyl groups, in excellent yields using cross-coupling reactions. 4-(2-Pyridyl)benzo[e]indoles, upon treatment with BF3·Et2O/Et3N, afforded a new type of fluorescent boron complexes with large Stokes shifts.