Hexagonal boron nitride (h-BN) particles including hollow spheres (with a proportion of similar to 30-40%) and nanotubes (10%) have been synthesized by using sodium fluoroborate and sodium azide at 450 degrees C for 20h. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) studies show that the as-obtained BN hollow particles are crystalline. The total specific surface area of the product calculated from Brunauer-Emmentt-Teller (BET) absorption measurement is 89.79 m(2)/g, indicating that it may be utilized as a promising candidate for hydrogen storage container or catalyst. Thermal gravimetric analysis (TGA) result reveals its excellent thermal stability below 800 degrees C. Its possible growth mechanism and the effects of reaction parameters were also briefly discussed. (C) 2009 Elsevier B.V. All rights reserved.