A novel reaction of TiCl4 and NaNH2 at 450degrees-500degreesC for 12-24 h was performed for the preparation of TiN nanocrystatline powders. Powder XRD patterns indicated that the as-synthesized powder was cubic-phase TiN with a lattice constant a = 4.225 Angstrom. Transmission electron microscopy images showed that the TiN powders consisted of uniform particles with an average diameter of 10-20 nm. The binding energies of Ti2P(3/2) and Nls core levels at the position of 455.50 and 396.96 eV, respectively, were detected by X-ray photoelectron spectra. Four peaks, related to transverse acoustic, longitudinal acoustic, second-order acoustic, and transverse optical (TO) modes of TiN , respectively, were observed in the Raman spectra of TiN particles. A very reasonable formation mechanism of TiN nanocrystalline powders was proposed.