The immobilisation of the pyrphos ligand has been extended from highly symmetric dendri-A C H T U N G T R E N N U N G mers to less regular structured hyperbranched poly-] complexes have been synthesised using poly(propylene imine) (PPI) and poly(amido amine) (PAMAM) dendrimers as supports bearing between 4 and 64 potential catalytically active sites at their periphery as well as pyrphos-RhA C H T U N G T R E N N U N G (NBD) complexes tethered to hyperbranched poly(ethylene imines) carrying on average 9 to 139 functionalities located throughout the whole supporting structure. These immobilised systems have been used as catalysts for the hydrogenation of Z-methyl a-acetamidocinnamate. With the PPI, PAMAM, and hyperbranched poly(ethylene imine)-bound pyrphos-RhA C H T U N G T R E N N U N G (NBD) omplexes as catalysts, hydrogenations were carried out in methanol, and a decrease in activity and selectivity was observed with increasing size of the macromolecular support. Furthermore, the polycationic catalysts were tested in a liquid/liquid-biphasic system consisting of the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate {[BMIM] [BF 4 ]} and isopropyl alcohol. Using the PPI-, PAMAM-, and PEI-immobilised systems, a strong negative "dendritic effect" with increasing molecular size was observed with respect to the catalytic activity, the stereoinduction, and the recyclability. The PPI-bound rhodium(I)-complexes of generations one and two showed good reusability; even after triple recycling, with no loss of activity or selectivity being noted. It has been demonstrated that in this case the catalytic behaviour of hyperbranched systems is essentially similar to that of the related dendritic model system.