The role of hydrogen in the catalytic amination of aliphatic alcohols is studied using the amination of ldodecanoi with dimethylamine on a supported copper catalyst as a model reaction. The experiments show that hydrogen acts as an inhibitor for catalyst deactivation. Temperature programmed desorption (TPD) and differential scanning calorimetry @SC) measurements indicate that the deactivation is caused by nitride formation on the copper surface.The nitride is formed by ammonia, originating from the simultaneously catalyzed disproportionation of the reactant amines. A similar deactivation mechanism is also likely to occur on other metallic amination catalysts, e.g., nickel and cobalt, as TPD and DSC investigations with these catalysts indicate.