A gold(III) complex of an N-heterocyclic carbene based hemilabile ligand with two pendant pyrazole arms (1,3-bis((1H-pyrazol-3-yl)methyl)-2,3-dihydro-1H-imidazole, LH) was synthesized. Complex [LAu(III)Cl-3] is an excellent catalyst for promoting dihydroalkoxylation at room temperature, even catalyzing this reaction at 0 degrees C. [LAu(III)Cl-3] is one of the most efficient catalysts reported to date for the spirocyclization of alkynyl diols. Furthermore, [LAu(III)Cl-3] catalyzed intra- and intermolecular hydroamination reactions, achieving good to excellent conversions. [LAu(III)Cl-3] is a more efficient catalyst than a gold(I) analogue, [LAu(I)Cl]. The dependence of the quantity of weakly coordinating anion [BAr4F](-) ((3,5-trifluoromethyl)phenyl borate) present on catalysis efficiency was probed for the dihydroalkoxylation reaction. X-ray diffraction analysis of single crystals demonstrated the solid-state structure of gold complexes [LAu(III)Cl-3] and [LAu(I)Cl], which displayed the expected square -planar and linear coordination geometries, respectively.