In order to solve the difficult problem in separation of homogeneous catalyst from the reaction mixture, heterogenized rhodium carbonyl complex catalyst for hydroformylation of olefins was prepared by copolymerization of functionalized 3-aminopropyltriethoxysalane with tetraethoxysalane (TEOS) via the sol-gel method. The catalyst was characterized by FT-IR, X-ray photoelectron spectroscopy (XPS), ICP and N, absorption. The activity, selectivity and stability of this catalyst for I-hexene hydroformylation have been examined. It was concluded the activity depended on the surface area of the catalyst matrix, which varied according to the pH in the sol-gel process. The conversion of I-hexene reached 98.8%, with a selectivity of 99.6% of aldehydes and the n/i ratio of 0.86 under optimized conditions. Furthermore, it showed excellent stability and reusability, the catalyst was used for six times without obvious loss of activity. (c) 2005 Elsevier B.V. All rights reserved.