Uniform CeO2 nanoparticles with diameter in the range of 13-17 nm were synthesized through a one-step rapid hydrothermal strategy. The characterization indicated that (2 2 0) surface is the majority of the exposed CeO2 surfaces. The reaction conditions including reactant amounts, reaction time were studied and optimized. The addition of hexamethylenetetramine is the key to the formation of (2 2 0)-dominated surface structure. The product shows better catalytic performance on CO conversion corresponding to the result of temperature-programmed reduction under a H-2 environment. (C) 2014 Elsevier Ltd. All rights reserved.