The influence of LiOH promotion on Co-based Raney-catalysts for the selective hydrogenation of butyronitrile to n-butylamine was explored. Doping with LiOH led to an increase in the fraction of metallic surface area and reduced concentration of Lewis acid sites resulting from alumina particles decorating the metal surface. Two factors were found to be crucial to achieving high selectivity to primary amines. These factors include a low adsorption constant of n-butylamine relative to butyronitrile (because adsorbed butylamine is necessary for byproduct formation) and a low concentration of Lewis acid sites catalyzing condensation reactions. (c) 2006 Elsevier Inc. All rights reserved.