SBA-15-based heterogeneous catalysts were applied to 1-octene hydroformylation. The turn over frequency over SBA-15/gamma-aminopropylmethyldimethoxysilane (AEAPMDMS)/Rh catalyst with triphenylphosphine (TPP) ligand prepared by conventional post grafting method was higher than that of the homogeneous catalyst, (Rh(CH3COO)(2))(2) with TPP. The SBA-15/AEAPMDMS/Rh catalyst can be easily recycled without rhodium loss. The molar ratio of linear to branched nonyl aldehydes was remarkably enhanced over the heterogeneous catalysts. The selectively functionalized rhodium catalyst (SBA-15/Ph2Si(OEt)(2)/AEAPMDMS/Rh), in which rhodium was selectively tethered intra-pore of SBA-15, was beneficial for improving the selectivity to linear aldehyde. In situ high pressure FT-IR analysis suggested HRh(CO)(2)(PPh3)(2) and HRh(CO)(PPh3)(3) to be active species over the SBA-15/AEAPMDMS/Rh catalyst with TPP. (C) 2010 Elsevier B.V. All rights reserved.