Different inorganic and organometallic gold(Ill) and gold(l) complexes have been tested in the addition of water and methanol to terminal alkynes. Anionic and neutral organometallic gold(Ill) compounds can efficiently mediate these reactions in neutral media in refluxing methanol. The compounds are added in catalytic amounts (1.6-4.5 mol % with respect to the alkyne). Thus, compounds of the general formula Q[AuRCl3], Q[AuR2Cl2], [AuRCl2](2), and [AuR2Cl](2) (Q = BzPPh(3)(+), PPN: N(PPh3)(2+) or N(Bu)(4)(+); R = C6F5 or 2,4,6-(CH3)(3)C6H2) seem to behave as Lewis acids in nucleophilic additions to triple bonds. Some intermediates could be detected in the stoichiometric reaction between [Au(C6F5)(2)Cl](2) and phenylacetylene that was followed by variable temperature H-1, F-19{H-1}, COSY F-19{H-1}-F-19{H-1}, and H-2{H-1} NMR experiments. Compound [Au(C6F5)(2)Cl](2) is also able to catalyze the hydration of phenylacetylene at room temperature. A plausible mechanism for the hydration reaction has been proposed.