The interaction of N2O with pure silver at temperatures up to 900 °C has been studied using temperature-programmed reduction and desorption; the interaction is compared with that of oxygen with silver. The effect of addition of N2O, as well as of the complete replacement of oxygen by N2O, on the oxidative dehydrogenation of methanol on a silver catalyst has also been studied. It was found that the interaction of silver with N2O was much slower than that of O2; no atomic surface oxygen species were observed, probably because the formation of subsurface species was not complete; selective adsorption appears to take place on the surface defects and grain boundaries involved in the formation of the subsurface species. Addition of small amounts of N2O to the reaction mixture (CH3OH + O2) for the oxidative dehydrogenation of methanol had almost no influence on the conversion or on the product distribution measured. However, the conversions were considerably lower when oxygen was totally replaced by N2O; only above 600 °C was the N2O exhausted. At the same level of conversion of the methanol, the amount of CO2 produced was lowered compared to the case of O2. This is in agreement with the suggestion that CO2 is formed via weakly bound surface oxygen.