We herein describe a practical direct amination of phenols through a palladium-catalyzed hydrogen-transfer-mediated activation method to synthesize the secondary and tertiary amines. In this conversion, environmentally friendly water and inexpensive ammonium formate were used as solvent and reductant, respectively. A range of amines, including aliphatic amines, aniline, secondary amines, and diamines, could be coupled effectively by this method to achieve mono/dual amination and cyclization of phenols. This study not only provides a green and mild strategy for the synthesis of secondary and tertiary naphthylamines but also expands the synthesis of chloroquine in organic chemistry.