A TEA-CO2 laser-induced breakdown technique was applied to synthesize fine powders of Band TiB2 by irradiating gas mixtures of BCl3+H2 and BCl3+TiCl4+H2 of 10-500 Torr. The products were characterized by SEM, ICP atomic emission spectroscopy and electron and X-ray diffraction. The particle sizes of the powders were controllable from 0.08 to 0.3μm by varying the total pressure of the mixed gas. The gas breakdown threshold energy of the laser pulse was found to be inversely proportional to the total pressure of the gas mixtures in a logarithmic scale, and the proportional constant was -0.52 for BCl3+H2. The yields of particles were increased with increasing laser pulse energy, whereas average particle size was constant.