Co-modified silicone oil with long-chain alkyl ester and epoxy ether (PEESO) was synthesized using hydrosilylation of poly (hydromethyl, dimethyl) siloxane (PHMS) with stearyl methacrylate (SMA), allyl epoxy (poly) ether in the presence of platinum ((trimethyl)cyclopentadienylplatinum) catalyst. The effect of reactive conditions，such as dosage of catalyst, molar ratio of reactants, reaction temperature and time, on the Si-H conversion rate was discussed well. By orthogonal experiment and the corresponding single factor experiments, the preferential experimental conditions were obtained as follows. The amount of catalyst is 0.004% of material mass, the molar ratio of PHMS and alkene compounds 1:1.05, the reaction temperature 72℃, reaction time 3h. The molecular structure of the product was determined by FTIR and 1H-NMR. The experimental results indicated that the chain of long-chain alkyl ester and epoxy (poly) ether is grafted in the chain of polysiloxane.