Mesoporous hollow α-Fe2O3 bricks were synthesized via a hydrothermal method to create a precursor MIL-100(Fe) and a subsequent calcination process was applied to prepare the Fe2O3 phase. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results showed the morphology of hollow α-Fe2O3 bricks which inherited from the MIL-100(Fe) template. The catalytic activities of hollow α-Fe2O3 bricks for CO oxidation are studied in this work. Due to better low temperature reduction behavior, mesoporous hollow α-Fe2O3 bricks obtained at calcination temperature of 430°C displayed high catalytic activity and excellent stability with a complete CO conversion temperature (T100) of 255°C.