Decomposition of cyclohexyl hydroperoxide (CHHP) is an important step in the preparation of cyclohexanol and cyclohexanone by non-catalytic oxidation of cyclohexane. Using Co₃O₄ nanoparticles as the core, cetyltrimethylammol/lonium bromide (CTAB) as the template and tetraethyl orthosilicate (TEOS) as the silicon source, the core-shell structure material Co₃O₄@SiO₂ was synthesized by template method. The effects of the preparation conditions for SiO₂ shells on the structure of core-shell material were investigated, such as the ratio of ethanol to water, the concentration of CTAB and the amount of TEOS. Textural properties of the materials were characterized by different techniques. Meanwhile, the catalytic performance and stability of the materials were evaluated on the decomposition reaction of CHHP. All results showed that the materials with thin shell and high porosity exhibited a preferable catalytic performance, and the conversion of CHHP was 81.68% and the selectivity of cyclohexanol and cyclohexanone was 70.60% and 34.06%, respectively. This core-shell structure could protect the activity of the core Co₃O₄ and significantly decrease the loss of cobalt element. However, there existed different degree of the fragmentation of SiO₂ shell in the recycling process of Co₃O₄@SiO₂ samples.