Three morphology controllable CeO 2 crystals were successfully synthesized via the thermal decomposition of CeCO 3 OH precursors, which was newly prepared on the basis of a simple and template-free hydrothermal reaction between CeCl 3 solution and a CO 2 -storage material (CO 2 SM). In the formation processes of three CeCO 3 OH precursors, the CO 2 SM could be newly used as raw material and structural director. Meanwhile, the results presented the wider pH values (5.24-8.35) for isoelectric point of CeCO 3 OH precursors. After the CeCO 3 OH precursors were isolated, the filtrate could be recycled to absorb CO 2 again and prepare CeCO 3 OH precursors with two special polymorphs. Three as-prepared CeO 2 crystals by annealing three CeCO 3 OH precursors at 500 8C for 4 h showed the maximum adsorption amounts of 23.5, 18.7 and 20.5 mg/g for 8% CO 2 /N 2 mixture. As a result, this work provided the wider pH values for isoelectric point of CeCO 3 OH precursors and a simple method for the preparation of CeO 2 crystals with a short time and CO 2 adsorption properties.