Co-entrapment of palladium nanoparticles and soluble [Rh(cod)(mu-Cl)](2) in a silica sol-gel matrix forms a catalyst that promotes exhaustive hydrogenation and hydrogenolysis of various aromatic ketones. While the hydrogenation of acetophenone may proceed by initial formation of alpha-phenylethanol followed by dehydration to styrene and further reduction of the olefinic and aromatic C-C bonds, the reaction of benzophenone and related compounds does not involve the intermediary of a carbinol. The immobilized combined catalyst is leach-proof and perfectly recyclable in at least five consecutive runs. Its unique catalytic activity is attributed to a synergistic effect between the different metal atoms. (C) 2002 Elsevier Science B.V. All rights reserved.