Using density functional theory, we examine the effects of a nitrogen atom adsorbed onto an anionic golden cage (Au16-) on the properties of the nanocage. For the exohedral adsorption that is more stable than the endohedral doping, the bridge and hollow sites have larger binding energies than the atop sites by ∼1 eV. When the N atom is adsorbed on the cage, electrons are transferred to nitrogen from Au16-. The nitrogen atom may move thermally from the exterior to the interior through a bridge site. In infrared spectra, exohedral doping causes greater intensities at higher frequencies than endohedral doping.