Indolyl enol ethers, generated from the alkoxy(indolyl)carbenium tetrafluoroborates 1 by treatment with sodium hydride, can be trapped with dimethyl acetylenedicarboxylate or N‐phenylmaleimide to furnish the selectively functionalized carbazoles 3,4,5,9,10, and 13. In addition, the biaryl derivatives 6 and 11 are produced by a ring‐opening reaction of the primarily formed Diels‐Alder adduct. In the case of the biaryl derivative 6, an X‐ray crystal structure analysis yields valuable information on constitutions and configurations in the biaryl series. The phenomenon of atropisomerism is discussed for this compound.