In this paper, poly(4vinylpyridine-co-styrene) (P(4VP-co-St)) was grafted on silica gel particles in the manner of "grafting from'', and the grafting particle P(4VP-co-St)/SiO2 was gained. The grafting particle P(4VP-co-St)/SiO2 is a novel kind of supports for immobilizing metalloporphyrin catalysts. Then, the immobilization of cobalt tetraphenylporphyrin (CoTPP) on the supports P(4VP-co-St)/SiO2 was carried out via the axial coordination reaction between CoTPP and the pyridine groups of the grafted P(4VP-co-St), resulting in the heterogenised catalysts CoTPP-P(4VP-co-St)/SiO2. The synthesized catalysts were characterized by FTIR and the axial coordination process between CoTPP and the grafted P(4VP-co-St) was confirmed by UV-vis. The effects of various factors on the immobilization reaction of CoTPP were studied in detail. Finally, the catalytic performance of CoTPP-P(4VP-co-St)/SiO2 in the catalytic oxidation process of ethyl benzene was investigated. The experimental results show that the axial coordination reaction is a very easy and novel method for favorably immobilizing CoTPP onto the P(4VP-co-St)/SiO2 surfaces. During the immobilization process of CoTPP on P(4VP-co-St/SiO2, the most bonding amount of CoTPP (0.19g/g) is obtained under the lower temperature (5 degrees C) and the higher concentration of CoTPP(6.0 mg/ml) lasting 4 h. Moreover, the supported catalyst CoTPP-P4VP-co-St)/SiO2 can effectively activate the dioxygen, and obviously catalyze the transform of ethylbenzene into acetophenone. So it exhibits the. ne catalytic activity. (C) 2008 Elsevier B. V. All rights reserved.