Ag supported on Co3O4 catalysts were prepared by facile one-pot solvotermal method. The obtained Ag/Co3O4 catalysts exhibited the excellent catalytic activity of benzene oxidation in comparison with Ag/Co3O4-I catalyst synthesized by the impregnation method. The characterization results revealed that Ag/Co3O4 catalysts possessed more surface active oxygen species and lattice defects, and exhibited the excellent low-temperature reducibility. The catalytic activity of benzene oxidation was in the order of 2%Ag/Co3O4 > 1%Ag/Co3O4 > 2%Ag/Co3O4-I > Co3O4. Accordingly, 2%Ag/Co3O4 catalyst exhibited the T-50 and T-90 values of 181 and 201 degrees C for benzene oxidation, which were lower than those of other catalysts. In addition, the catalysts exhibit the outstanding long-term thermal stability.