We demonstrate a supercritical CO 2 (scCO 2 ) deposition method to synthesize mesostructured Co 3 O 4 with crystalline walls using SBA-15 as the hard template. By variation of the scCO 2 pressure, randomly organized nanorods or a highly ordered mesoporous structure of Co 3 O 4 is obtained after only one filling operation. The catalytic tests show that the randomly organized Co 3 O 4 nanorods display excellent activity for CO oxidation with the complete conversion of CO even at room temperature, while neither the ordered mesoporous nor bulk Co 3 O 4 is active at this low-temperature, demonstrating the important role of Co 3 O 4 morphology in catalysis.