Abstract: Hydroformylation of 1-hexene over a series of silica supported noble metal catalysts，HRhCO（TPP）3，HRhCO（TPPTS）3/SiO2 and TPPTS-Rh/SiO2 catalyst were investigated. The results show that the selectivity towards aldehydes and the ratio of liner to branched aldehyde（ n/b）over Rh-TPPTS / SiO2 catalyst are near to those of HRhCO（TPPTS）3/SiO2，but much higher than to those of Rh/SiO2 . Under the higher pressure of 7.0 MPa，the TOF of aldehydes on Rh-TPPTS / SiO2 catalyst increase greatly up to 0.0692 S-1 . A possible of catalyst model of Ligands containing lone-pair electron tightly chemically connected to the highly dispersed Rh particles and formation of supported aqueous-film heterogeneous catalyst possessing of homogeneous catalytic performance has been tentatively proposed.