In this study, cobalt tetraphenylporphyrin was immobilized through amide bond on organosilicon microsphere mixed with ceria. The catalysts were characterized and the catalytic performance was investigated. The results show that the catalysts are nanoparticles with average sizes of 30 nm and organosilicon microsphere is mixed with ceria. In addition, the catalysts exhibit excellent catalytic performance for selective oxidation of cyclohexane by molecular oxygen without solvent in a sealed autoclave reactor, due to the cooperative effect among the metalloporphyrin, organosilicon microsphere and ceria. The conversion of cyclohexane and the selectivity of cyclohexanol + cyclohexanone reached 14.21% and 54.6%, respectively. After repeated reuse, the conversion of cyclohexane and the selectivity of cyclohexanol + cyclohexanone were still kept at about 13.1% and 61.9%, respectively. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.