The discovery that supported gold clusters act as highly efficient catalysts for low-temperature oxidation reactions has led to a great deal of work aimed at understanding the origins of the catalytic activity. Several studies have shown that the presence of trace moisture is required for the catalysts to function. Using near-atmospheric pressure flow reactor techniques, we have studied humidity and temperature effects on the reactivity of gas-phase gold cluster anions with O-2. Near room temperature, the humid source produces abundant gold-hydroxy cluster anions, AuWOH-, and these have a reversed O-2 adsorption activity: Nonreactive bare gold clusters become active when in the form AuWOH-, while active bare clusters are inactive when -OH is bound. The binding energies for the stable structures obtained from density functional calculations confirm fully these findings. Moreover, the theory provides evidence that electron-transfer induced by the binding of a OH group enhances the reactivity toward molecular oxygen for odd anionic gold clusters and suppresses the reactivity for the even ones. The temperature dependence of O-2 addition to AU(3)OH(-) and AU(4)(-) indicates deviations from equilibrium control at temperatures below room temperature. The effects of humidity on gold cluster adsorption activity support the conclusion drawn for the mechanism of O-2 adsorption on "dry" gold cluster anions and provides insight into the possible role of water in the enhanced activity of supported gold cluster catalysts.