A tethered ligand-modified Rh/SiO2 Catalyst Was developed for hydroformylation with high stability. The catalyst was prepared by fastening both organic ligand and metal directly on the surface of support to avoid leaching, while at the same time the active species were formed in situ by coordination of the flexible ligand to the metal on the surface Of SiO2. The immobilization of ligand on SiO2 and the interaction between ligand and metal were investigated by means of TG, solid-state NMR and FTIR. Hydroformylation of ethylene was selected as a probe reaction to evaluate the immobilization and coordination of ligand to the nano-metal particles. High activity and excellent stability were observed during a 1000-h run. (C) 2008 Elsevier B.V. All rights reserved.