Adiponitrile was hydrogenated to hexamethylenediamine in a three phase stirred slurry reactor at 353 K and 3 MPa using rhodium on gamma-alumina powder as a catalyst. Rhodium, with a very high metal dispersion, was deposited on the alumina support using the metal vapour synthesis technique. The performances of this supported catalyst were compared to those of one currently used in industrial processes (Raney Ni). The Rh/Al2O3 catalyst showed interesting hexamethylenediamine selectivity and adiponitrile conversion. Both the temperature and pressure positively influenced conversion and selectivity, and under a certain pressure threshold the formation of hexamethylenediamine was negligible. (C) 2003 Elsevier B.V. All rights reserved.