A method for selective liquid-phase heterogeneous catalytic hydrogenation of nitriles to primary amines has been developed. Benzyl cyanide (BC) was hydrogenated under mild reaction conditions (40 degrees C, 6 bar), over a carbon supported palladium catalyst, in a mixture of two immiscible solvents (e.g. water/dichtoromethane) and in the presence of an acidic additive (e.g. NaH2PO4). Complete conversion, but lower isolated yield (40%) and selectivity (45%) to primary amine could be achieved by using this process than in the hydrogenation of benzonitrile (BN) reported previously. A comparison concerning the reactivities and adsorption abilities of these substrates (BC and BN) was also made. (c) 2008 Elsevier B.V. All rights reserved.