Gold (Au) is an interesting catalytic material because of its ability to catalyze reactions, such as partial oxidations, with high selectivities at low temperatures; but limitations arise from the low O(2) dissociation probability on Au. This problem can be overcome by using Au nanoparticles supported on suitable oxides which, however, are prone to sintering. Nanoporous Au, prepared by the dealloying of AuAg alloys, is a new catalyst with a stable structure that is active without any support. It catalyzes the selective oxidative coupling of methanol to methyl formate with selectivities above 97% and high turnover frequencies at temperatures below 80 degrees C. Because the overall catalytic characteristics of nanoporous Au are in agreement with studies on Au single crystals, we deduced that the selective surface chemistry of Au is unaltered but that O(2) can be readily activated with this material. Residual silver is shown to regulate the availability of reactive oxygen.