Novel chiral ligands (2S,4R)-2-(t-butylaminocarbonyl)-4-[3-(alkylaminocarbonyl)propanoyloxy]pyrro lidine and (2S,4S)-cis-4-(alkylaminocarbonylamino)-2-(t-butyl-aminocarbonyl)pyrrolidine (4a,b; 9a,b), (a: alkyl = t-butyl; b: alkyl = 3-triethoxysilylpropyl) and their rhodium complexes were synthesised and characterised. The reactions of [{Rh(cod)Cl} 2 ] and [RhCl(PPh 3 ) 3 ] with the chiral ligands in the presence of a non-coordinating anion (PF - 6 ) gave the cationic complexes [Rh(L 2 )(ligand)][PF 6 ] (L 2 = cod, PPh 3 ). The structures of these complexes were elucidated by elemental analyses, IR spectroscopy and 1 H, 1 3 C and 3 1 P NMR measurements. The metal complexes bearing a triethoxysilyl group were covalently bonded to silica and modified USY-zeolite and Rh-heterogenised complexes were obtained. A comparative study (homogeneous versus supported) was made for the catalytic activity in hydrogenation reactions.