Trimethoxyborane (B(OMe)(3)) was confirmed to be an effective precursor for the preparation of spherical boron nitride (BN) particles in the presence of ammonia. The spherical particles with the uniform diameter distribution and smooth surface were synthesized by the chemical vapor deposition (CVD) route, and then novel fluffy-like BN spheres were prepared by using the as-prepared BN ones as CVD substrates. The microscopy and spectroscopy examination indicated that the spheres consist of smooth core and fluffy shell. The second growth induced abundant defects at the surface of the fluffy BN spherical structure. which is important for the novel materials as a catalyst support with high loading amount of metal. (C) 2008 Elsevier B.V. All rights reserved.