Three different morphologies of hexagonal boron nitride (h-BN) are exhibited in this paper. The h-BN morphology was changed from needle-like to an irregular sheet and hollow spherical in the presence of a silane coupling agent. These products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transformation infrared spectroscope (FT-IR), Brunauer-Emmett-Teller procedure (BET) and thermogravimetric analysis (TGA). The hollow spherical h-BN could be obtained under mild conditions and the size of spherical h-BN could be controlled under different temperatures. (C) 2010 Elsevier B.V. All rights reserved.