Oxygen vacancies can capture and activate gaseous oxygen, forming surface chemisorbed oxygen, which plays an important role in the Hg0 oxidation process. Fine control of oxygen vacancies is necessary and a major challenge in this field. A novel method for facet control combined with morphology control was used to synthesize Co3O4 nanosheets preferentially growing (220) facet to give more oxygen vacancies. X-ray photoelectron spectroscopy (XPS) results show that the (220) facet has a higher Co3+/Co2+ ratio, leading to more oxygen vacancies via the Co3+ reduction process. Density functional theory (DFT) calculations confirm that the (220) facet has a lower oxygen vacancy formation energy. Furthermore, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results suggest that Co3O4 nanosheets yield more defects during the synthesis process. These results are the reasons for the greater number of oxygen vacancies in Co3O4 nanosheets, which is confirmed by electron energy loss spectroscopy (EELS), Raman spectroscopy, and photoluminescence (PL) spectroscopy. Therefore, Co3O4 nanosheets show excellent Hg0 removal efficiency over a wide temperature range of 100-350 °C at a high gas hourly space velocity (GHSV) of 180 000 h-1. Additionally, the catalytic efficiency of Co3O4 nanosheets is still greater than 83%, even after 80 h of testing, and it recovers to its original level after 2 h of in situ thermal treatment at 500 °C.