A series of 1,2,3-triazole-bound cationic Au(I) catalysts have been synthesized, and their structures have been characterized by X-ray crystallography. Variable-temperature NMR studies revealed dynamic triazole-Au cation coordination in solution. Reaction profiles clearly indicated that these new catalysts possess much better thermal stability than literature-reported Au catalysts, including IPrAu center dot NT2(f). By application of these catalysts, challenging intermolecular hydroaminations were achieved with less-reactive internal alkynes and unprotected aliphatic amines, giving excellent yields with low catalyst loading.