Single-phase bismuth ferrite (BiFeO3) powders were synthesized with a hydrothermal method by controlling the experimental conditions carefully. The powder structure, morphology and composition were characterized by using X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscope, Raman measurement and X-ray photoelectron spectroscopy. The particles change from irregular agglomerations to regular cubes with increasing KOH concentration. The large BiFeO3 cubic particles enjoy much smooth surfaces with well-matched element ratio (Bi:Fe:O = 1:1:3) and chemical valence (Bi3+, Fe3+ and O2-). The high temperature XRD and differential scanning calorimetry show that BiFeO3 powders have a hexagonal perovskite structure with a space group R3c below 370 degrees C and a rhombohedral structure with a space group R3m below 755 degrees C. BiFeO3 undergoes a phase transition in the temperature range of 755-817 degrees C from rhombohedral structure to a cubic phase, then decomposes to liquid and Fe2O3 above 939 degrees C. (C) 2012 Elsevier Ltd. All rights reserved.