Disclosed is a method of synthesizing nano-sized tungsten-silica core-shell particles by a silica-based sol-gel process. According to the method, tungsten-silica nanoparticles are very easy to synthesize by a simple process at ambient pressure and temperature. In addition, tungsten oxide-silica (WOx@SiO2) nanoparticles including tungsten in a stable oxidation state can be synthesized. In the tungsten oxide-silica nanoparticles, the size of the tungsten protected with the silica shell can be maintained in the nanometer range without further processing. Also disclosed is a method of synthesizing nano-sized tungsten oxide (WOx) and tungsten carbide (WC) particles by further processing of the tungsten-silica core-shell particles.