The olivine-like material LiFePO4 was prepared via a continuous hydrothermal synthesis process working from subcritical to supercritical water conditions. The influence of some processing parameters-temperature and reaction time-was investigated in terms of material purity, grain size and morphology. Supercritical conditions were found to be attractive to synthesize in one step a well-crystallized material without impurities. The primary particles size was in the nanometric range. They showed a natural tendency to form micron size agglomerates, which were supposed to be the cause of the limited capacity, as demonstrated through a cross study using laser particle size distribution analysis, electrochemical measurements and XRD at different Li contents. (C) 2009 Elsevier B.V. All rights reserved.