The Bucherer reaction is a common pathway for the conversion of 1‐ and 2‐naphthols into the corresponding 1‐ or 2‐naphthylamines, respectively. Mostly, only singular examples for its preparative use are reported since this particular transformation seems to be very sensitive to the reaction conditions. By choosing different phenolic substrates and chiral amines, we were able to prepare a broad scope of optically pure arylamines using this type of reaction. In contrast to alternative methods forming C−N aryl bonds such as Buchwald‐Hartwig or Chan‐Lam cross‐coupling reactions, no palladium or copper catalysts are required. The use of water as solvent and the easily available starting materials make this method to an attractive approach. Using the Bucherer reaction to synthesize optically pure arylamine derivatives depicts an elegant alternative to transition‐metal or copper‐catalyzed reactions. We prepared 15 arylamine derivatives using this reaction. The desired products can be obtained in yields up to 70 %.