Cubic-like CeO2 nanocrystals were successfully synthesized through an improved-toluene solvothermal process using hexadecylamine (HAD) as a capping agent and CeCl3 center dot 7H(2)O as a precursor at 180 degrees C for 24 h. These nanocubes are about 10 nm in size, and have a tendency to assemble into 2D superstructure. The obtained samples were characterized by means of X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). It was found that the water content, the concentration of ligand and kinds of aliphatic amine played important roles in the formation of the novel morphology. A possible formation mechanism was proposed based on the controlling reaction parameters. The electrochemical and photocatalytic properties of the as-synthesized samples exhibited the size/shape-dependent properties and potential applications. (C) 2009 Elsevier B.V. All rights reserved.