A benzene-thermal reaction of TiCl4 and NaN3 at 350 degrees-380 degrees C was conducted for the preparation of nanocrystalline TiN, Powder X-ray diffractometry patterns indicated that the powder was cubic-phase TIN with a lattice constant a = 4.23656 A. Transmission electron microscopy images showed the TiN powders consisted of uniform spherical particles with an average diameter of 50 nm, The binding energies of Ti 2p3/2 and N Is core levels at the positions of 454.85 and 397.1 eV, respectively, and the Ti:N atomic ratio of 1.08:1.00 were detected by X-ray photoelectron spectra, A possible formation mechanism of TiN was proposed.