It is shown that Ag/Al2 O3 is a unique catalytic system for H2 -assisted selective catalytic reduction of NOx by NH3 (NH3-SCR) with both Ag and alumina being necessary components of the catalyst. The ability of Ag/Al2O3 and pure Al2O3 to catalyse SCR of mixtures of NO and NO2 by ammonia is demonstrated, the surface species occurring discussed, and a “Fast SCR”-like mechanism of the process is proposed. The possibility of catalyst surface blocking by adsorbed NOx and the influence of hydrogen on desorption of NOx were evaluated by FTIR and DFT calculations.