Nanocrystalline TiC hollow polyhedrons have been prepared at 500 degreesC by the reaction of TiCl4 and CaC2. Crystalline CaC2 particles with high melting point act not only as the reactant but also as the templates. X-ray powder diffraction indicates that the product is cubic TiC with a lattice constant a = 4.314 Angstrom Transmission electron microscopy manifests that the polyhedrons are 30-60 nm in size. The formation mechanism of the polyhedrons is discussed. (C) 2004 Elsevier B.V. All rights reserved.