Eight metal cluster compounds have been synthesized from parent compound （μ3-CPh）Co3-（CO）9 and triphenylphosphine（arsine,stibine,bismuthine）. All the compounds were characterized by elemental analysis and IR spectrometry. They results showed that their catalytic activities for 1-butene hydroformylation and the yields of product both were higher than that of the parent compound in 97% and 20% more, respectively, at reaction conditions of 303.5 K, 0.392 MPa, and for 48 hours. The catalytic activities and the ratio of nor to iso by using PhCCo3（CO）7（APh3）m were increased with increase in the atomic numbers of element A（A=P,As,Sb,Bi）.
