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We studied the aerobic oxidation of methanol over nanoporous gold catalysts under neutral and alkaline conditions. We find that under neutral conditions the catalyst has an activation period of about 10 h while upon addition of a base the catalyst becomes active right away. After this activation period, however, the activity of the catalyst is in both cases similar. Moreover, the selectivity was not affected by the base. We tested different bases and found the largest effect when adding OH−. The cation, however, does not play a role. We conclude that it is OH−, which is impacting the reaction and propose a mechanism for the suppression of the activation period. While the catalytic cycle, i.e., the reaction of methanol on the catalyst surface seems unaffected, the transient adsorption of OH− onto the surface can facilitate the activation of molecular oxygen by donating electrons to the surface. Due to the intermediate formation of oxidic Ag species, an effective segregation of surface-near Ag can be induced, which increases the abundance of Ag being essential for the activation of oxygen at the surface. In this way, a more efficient pathway for the generation of active oxygen is opened, allowing the reaction to set in faster.