The change in the electronic structure of Au-n(-) clusters induced by the exchange of an Au atom by hydrogen is studied using photoelectron spectroscopy. Au anion clusters react with one hydrogen atom but not with molecular hydrogen. The spectra of Au-n(-) and Aun-1H- clusters show almost identical features for n > 2 suggesting that hydrogen behaves as a protonated species by contributing one electron to the valence pool of the Au-n(-) cluster. This behavior is in sharp contrast to that of the commonly understood electronic structure of hydrogen in metals; namely, it attracts an electron from the conduction band of the metal and remains in an "anionic" form or forms covalent bonding. We discuss the influence of the unique electronic structure of H on the unusual catalytic behavior of Au clusters.