POM-LDHs with the composition of MAI-XW11ZO39(M=Zn, Mg; X=P, Si; Z=Mn2+, Fe2+, Co2+, Ni2+, Cu2+) were synthesized, and their catalytic properties for oxidation of cyclohexene in the presence of dioxygen were studied. The results obtained show that the oxidation of cyclohexene gives mainly α-H oxidation products, and the reaction activities greatly depend on the nature of the substituted transition metals in the POM pillars, i. e.,with different Z ions, the activity is in the order: Co2+~Cu2+~Mn2+》Ni2+~Fe2+. In addition, the central atom in the POM pillars has some effects on the oxidation of cyclohexene.The activity increases when P is used instead of Si. No obvious difference between the activities of ZnAl and MgAl layers were observed.