The powder X-ray diffraction experiments of LiV2O4 have been performed at low temperature and high pressure using synchrotron radiation. In the isothermal experiment at 10 K, the cubic-rhombohedral phase transition corresponding to the metal-insulator transition is found at around 13 GPa. This transition seems to be due to charge ordering of V ions on the analogy of the metal-insulator transition in AlV2O4. (c) 2005 Elsevier B.V. All rights reserved.