Two different hollow structured Co3O4 micro-polyhedrons, derived from Zeolitic imidazolate frameworks (ZIF)-67 crystals, were fabricated by tuning the synthetic strategy (positive or reverse addition). The results demonstrate that the synthetic strategy significantly affect catalyst structure and properties. Compared with Co3O4-A nanocatalyst, the Co3O4-B nanocatalyst exhibit superior catalytic performance, showing 100% CO conversion at the conditions of T = 110 degrees C and SV = 30,000 h(-1). The higher catalytic performance could be attributed to its higher surface area, lower temperature reducibility, and abundant surface Co3+ and adsorbed oxygen.