The ultrafine titanium carbonitride particles () below 100nm in mean size were successfully synthesized by Mg-thermal reduction process. The nanostructured sub-stoichiometric titanium carbide () particles were produced by the magnesium reduction at 1123K of gaseous and the heat treatments in vacuum were performed for five hours to remove residual magnesium and magnesium chloride mixed with . And final phase was obtained by nitrification under normal gas at 1373K for 2 hrs. The purity of produced particles was above 99.3% and the oxygen contents below 0.2 wt%. We investigated in particular the effects of the temperatures in vacuum treatment on the particle refinement of final product.