The synthesis of nano-size tungsten carbide powder has been investigated with a WO3 Mg C carbonate system using alkali halides. The effects of different types of alkali halides on combustion temperature and tungsten carbide formation were discussed. Sodium fluoride had a notable effect on the particle size of the product and the degree of transformation from the initial mixture. A small amount of ammonium carbonate activated the carburization of tungsten carbide by the gas phase carbon transportation. X-ray diffraction data and particle analysis showed that the final product synthesized from a WO3–Mg–C–(NH4)2CO3–NaF system contains pure-phase tungsten carbide with a particle size of 50–100 nm.