The hydrothermal method is widely applied in nanomaterials synthesis, and most of the influencing factors have already been taken into account. However, the effect of atmosphere in solution on the performance of nanomaterials has been underestimated for a long time. In this article, reaction solvents were saturated with three classical gases (argon, oxygen, and carbon dioxide), and then heated at 180 8C for 24 h to obtain the cerium dioxide (CeO 2 ) nanoparticles. The properties of the three types of CeO 2 are significantly different from that of the normal CeO 2 (without gas saturation). The morphologies of the prepared CeO 2 particles are different, even appear the hollow structure in CeO 2 ÀCO 2 (synthesized in CO 2 saturated condition). The more absorbing and meaningful thing is that the photocatalytic activity of CeO 2 ÀCO 2 has been greatly improved. The concordance of the CO 2 atmosphere (acid gas) and CeO 2 (owning substantial content of basic sites) is the key point for the excellent photocatalytic performance.Cerium oxide (CeO 2 ) is one of the most important earth metal oxides. Due to the unique optical, electrical, magnetic properties and the oxygen storage capacity (OSC) of CeO 2 nanomaterials, [1] they have been used in various applications, in industrial and commercial fields, including solid oxide fuel cells (SOFCs), [2] purification of automobile exhaust, [3] abrasives for chemical mechanical polishing (CMP), [4] and photocatalysis. [5,6] In order to obtain nanoscale CeO 2 materials, researchers have explored a lot of synthesis strategies, including ball milling, electrochemical, templates assisted, sol-gel, hydrothermal, chemical vapor, and other methods. [1] A hydrothermal method is also suitable for the growth of good-quality crystals because this method over other types of crystal growth is the ability to create crystalline phases which are not stable at the melting point. A hydrothermal reaction is governed by various chemical and thermodynamic parameters, involving chemical composition of the precursor, [7] kind of solvent, [5] pH value of the reaction medium, [8] reaction temperature, duration of reaction, and pressure. Moreover, other associated technologies, such as microwaves, electrochemistry, external magnetic field, and ultrasound, have been employed However, an important factor in a hydrothermal process, the atmosphere of the solution, may be ignored by people. For a long time, the effect of the atmosphere on the hydrothermal process has been underestimated due to its extremely little content in the solution. Nevertheless, the solution in a hydrothermal process is boiling or gas phase. The atmosphere will have a significant effect on the final products. If the precursors and solvent are matched with the selected gas (Gas can be strongly absorbed on the precursors or solvent.), the crystal growth process would be altered and further affect their morphologies and performances.Herein, we selected three typical gases, argon, oxygen and carbon dioxide, to determine the relationship betwe...