The use of a versatile N-heterocyclic carbene (NHC) gold(I) hydroxide precatalyst, [Au(OH)(IPr)], (IPr=N,N'-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) permits the in situ generation of the [Au(IPr)](+) ion by simple addition of a Brønsted acid. This cationic entity is believed to be the active species in numerous catalytic reactions. (1)H NMR studies in several solvent media of the in situ generation of this [Au(IPr)](+) ion also reveal the formation of a dinuclear gold hydroxide intermediate [{Au(IPr)}(2)(μ-OH)], which is fully characterized and was tested in gold(I) catalysis.