Herein, hollow multishelled structure (HoMS) of Co3O4-CeO2-x nanocomposites with controllable molar ratio of Co and Ce elements is synthesized by a general strategy sequential templating approach (STA) with a facile and efficient electrostatic spray process. As a catalyst of carbon monoxide (CO) catalytic oxidation, Co3O4-CeO2-x (Co/Ce = 4/1) HoMS achieves good catalytic activity (complete conversion temperature is 166.9 degrees C) and stability (100 h). This performance is attributed to synergistic effects between the two components. The combination of Co3O4 and CeO2 not only generates more interfaces of Co3O4-CeO2-x, which is more favorable for the activation of oxygen, but also improves the oxidizability of Co3O4 as well as the capacity of oxygen storage of CeO2. In addition, the relatively larger effective specific surface area of the HoMS can provide more active sites, while the unique structure of HoMS can facilitate gas diffusion and maintain structural stability.